Supplemental Material NANOSH dataset - Springer …10.1007... · Web viewFigure. Distribution of NOAA(groups) produced or used in the different workplaces: High Aspect Ratio Nanoparticles

SUPPLEMENTARY MATERIAL

Brouwer D.H. et al. Workplace Air Measurements…. J. Nanopart. Res. NANO-D-12-06483


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

1



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

2



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

3



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

4



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)

5




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)


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

6



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)


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


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)


Instrument-group

< 100 nm

> 100 nm

Total* < 100 nm

> 100 nm

total

7



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


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


26900 2717 3639 5238-15940 15

Aerotrak X X X X 6.0-27.0 X 9

Burning of foam


Instrument- group

< 100 nm

> 100 nm

Total < 100 nm

> 100 nm

Total

Down-stream-use of ENP – non-commercial scale

8



SMPS 21281-380494

3272-26214

24553-401097

2440-23227

679-3081

3207-26350 6


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

9



(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

10



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

11



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.

12



HARNs

13



14



15



16



17



18



19



20



21



22



23



24



25



26



27



28



29



30



31



32



33



34



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





All n=118 n=45(38%) n=54 (46%) n=19 (16%)

35



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.

36



37



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.

38



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


sized particles

none

1

few

1

many

X


X

few

X

many

X


X

compacted bound

1

Aggregates non

X

few

1

many

1

Configuration fiber plates spherical particles

39



X X 1

Activities + non-activities (n=13)Particle type Frequency of observation


sized particles

none

13

few

1

many

X


X

few

X

many

X


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


sized particles

none

X

few

1

many

X


X

few

X

many

1


1

compacted bound

1

Aggregates non

1

few

X

many

X

Configuration fiber

X

plates

X

spherical particles

1

40





sized particles

none

2

few

3

many

X


X

few

X

many

X


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


sized particles

none

5

few

5

many

3


1

few

6

many

6


X

compacted bound

1

Aggregates non

1

few

8

many

4

Configuration fiber

3

plates

X

spherical particles

3

41





sized particles

none

X

few

4

many

2


X

few

X

many

X


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


sized particles

none

5

few

6

many

X


1

few

4

many

5


6

compacted bound

6

Aggregates non

2

few

4

many

X

Configuration fiber

X

plates

2

spherical particles

2

42





sized particles

none

1

few

2

many

X


X

few

X

many

X


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





All n=23 2 2 19

43



ScenarioScenarios measured during activity period





All n=40 8 5 27

ScenarioScenarios measured during non-activity period


44



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

45



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

46



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


Burning of foam 16410 7141 7536 26214 6


Scooping powder (small amounts)

825 688 120 1703 5

Various tasks 1166 371 694 1660 7


3650 3245 523 12993 18

47



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


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

48



Grinding powder 4 15 3 3 0


19 41 4 21 8

Mixing powder into liquid

4 13 3 4 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

49



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, 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


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)

50



51



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

52



LQ1Ventilation N Mean

(um2/cm3)std min


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


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

53



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)

54



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

55

Documents

Supplemental Material NANOSH dataset - Springer …10.1007... · Web viewFigure. Distribution of NOAA(groups) produced or used in the different workplaces: High Aspect Ratio Nanoparticles