THE NANOSAFER V1.1 RISK ASSESSMENT AND MANAGEMENT TOOL

–OVERALL SENSITIVITY ANALYSIS AND

ASSESSMENT OF THE MODEL PERFORMANCE

Keld Alstrup Jensen (kaj@nrcwe.dk)

Dansk Center for Nanosikkerhed

Det Nationale Forskningscenter for Arbejdsmiljø

København, Danmark

NanoSafer 1.1beta (www.nanosafer.org)

Currently applicable for MNM powder handling

and processes with constant source MNM emission rates

Key elements and information requirements in the Control Banding models

Method

Number of

Input

parameters

asked for

Number of

input parameters used

Number of

control bands

Nano-

relevance

Hazard

scaling

Expo.

scalingHaz. Exp. Risk

ANSES CB Tool ¤ 9 1 5 3 5 4 5

NanoSafer 1.0 # 25 5 5 13 4 5 5

IVAM Guidance ¤ 28 - 2 1 3 3 3

Swiss Precautionary Matrix 28 7 6 6 n.a. n.a. 2

CB Nanotool 53 - 15 5 4 4 4

Stoffenmanager Nano # 47 - 2 26 5 4 3

Modified from Liguori et al. (2016)

¤ The technically simplest model

# The technically most advanced models

Four Assessments in “One Go”(Near-Field and Far-Field – Acute and Daily)

Hazard Assessment- Example with R-sentences

“nanorelevance”

NM with low

solubility (So < 1 g/L)

Is the NM a HARN

(a < 3 µm c > 5 µm

c/a > 3)

traditional risk

assessment is suggested

Htot = 1.00

Hcoat = 0.45

yes

no

yes

yes

yes

no

Are there any R-phrases

for the analogue bulk material

HOEL = 0.20

no

yes

Is the OEL for the analogue

bulk material < 1 mg/m3?

Is the NM surface modified

with an inorganic

and/or organic compound?

no

no

Calculate Htot

jij

n

i itot HHH 11

HOEL = 0.26

Calculate accumulated

HR from R-values

ij j

n

i icarc RRH 11

Rj [0.1;1] for each Hi

Hi = General tox and CMAR

Examples of MNM Hazard Ranking Compared to OELs of analogue bulk materials

Material SSA

[m2/g] HARN Coated

OEL

[mg/m3] Ri

TiO2 21 - 0.45 10.0 -

TiO2 107 - 0.45 10.0 -

ZnO 12.4 - - 4.98 -

ZnO 15.1 - 0.45 4.98 -

graphite 225 - - 3.50 -

carbon black 23.8 - - 3.50 -

carbon black 295 - - 3.50 -

Kaolin 23.1 - - 2.50 -

nanoclay 8.44 - 0.45 5.00 -

SWCNT-OH 407 - 0.45 3.50 R36/R37

MWCNT 233 1 - 3.50 R36/R37

Fe2O3 27.4 - - 5.00 R36/R37/R8

Fe2O3 27.7 - - 5.00 R36/R37/R8

NiFe2O4 87.7 - - 0.200 R43/R49

Ni0.5Zn0.5Fe2O4 104 - - 0.203 R43/R49

NiO 6 - - 0.064 R49/R43/R53

Co(10% O passivated) 60 - - 0.010 R11/R42/R43/R53

Ag 0.03 - 0.45 0.010 -

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

0.01 0.1 1 10

OEL [mg/m3]

Hazard

Sco

re;

Hto

tal

AgNP(PVP)

SWCNT-OH

MWCNT

H1

H2

H3

H4

Fe2O3

Organoclay/

coated ZnO

coated TiO2

NiO NiFe2O4/

NiZnFe4O8

Co

kaolinite

CB/graphiteZnO

Exposure Assessment and Scaling- Example of using Powders

CNF

QNF

Source

Emission rate:

Ei = Eo x Ai x dM/dtEi = release rate

Eo = dustiness index

Ai = activity energy factor

Ao: ”zero” (clean transport)

A1: very low (weighing mg’s)

A2: low (< 5 cm drop)

A3 : moderate (5-30 cm drop)

A4 : high (30-100 cm drop)

A5 : very high (> 100 cm drop)

dM/dt = mass flow rate

Exposure Assessment and Scaling- Example of using Powders

FF

Far-Field

NF

Ei

Near-Field

Far-Field

CFF

CNF

Cout = 0

CFF

1,,

tNF

NF

FFNFNFFF

NF

itNF R

V

MMt

V

EC

1,,

tFF

FF

NFFFFFNFtFF R

V

MMC

1

2

t

NF

NF

NFFFNFNFFF

NFett

VCM

1

2

t

NF

NF

NFNFNFFFNF

NFett

VCM

t

FF

tNF

tNFFFe

t

CR

1

1,

1,

t

FF

tFF

tFFFFe

t

CR

1

1,

1,

Dispersion model:

Where M and R are:

Exposure scaling

NF Acute (15 min): Upper limit is 2 xOELnano

NF Daily (8-hour): Upper limit is OELnano

FF Acute (15 min) : Upper limit is 2 xOELnano

FF Daily (8-hour) : Upper limit is OELnano

NF volume = 12.17m3 (2.33 m3)

Exposure scale: Ci / OELnano

OELnano = OELbulk x (VSSAnano / VSSAbulk)

Aerosol decay functions after Schneider et al. (2004)

Exposure Assessment and Scaling- Example of using Powders

0.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

-0.5 0.5 1.5 2.5 3.5

Time [hours]

Resp

irab

le I

mm

issio

n P

ote

nti

al

[mg

/m3]

C(NF) - RDI-SC(NF) - UV-Titan L181C(NF) - NM-110 (ZnO)C(NF) - NM-111 (f-ZnO)C(NF) - GraphiteC(NF) - Flammrüss 101C(NF) - Printex 90C(NF) - ASP-90C(NF) - Nanofil®5C(NF) - Fe2O3*C(NF) - NiFe2O4C(NF) - Ni0.5Zn0.5Fe2O4C(NF) - AgNPC(NF) - CNT-NiO-Co

0

0.2

0.4

0.6

0.8

-0.5 0.5 1.5 2.5 3.5

Time [hours]R

esp

irab

le I

mm

issio

n P

ote

nti

al

[mg

/m3]

C(FF) - RDI-SC(FF) - UV-Titan L181C(FF) - NM-110 (f-ZnO)C(FF) - NM-111 (f-ZnO)C(FF) - GraphiteC(FF) - Flammrüss 101C(FF) - Printex 90C(FF) - ASP-90C(FF) - Nanofil®5C(FF) - Fe2O3*C(FF) - NiFe2O4C(FF) - Ni0.5Zn0.5Fe2O4C(FF) - AgNPC(FF) - CNT-NiO-Co

Scooping/filling 5 x 500 g bags in small scale production:

Total mass: 500 g

Mass per transfer (spoonful): 50 g/scoop.

Hi = 0.3

Duration per filling: 10 minutes

Duration per transfer: 0.5 minute

Pause between each filling: 5 minutes

Work area: 3.5 m x 5 m long x 2.9 m high

ventilation rate of 5 h-1

Variation reflects variation

in dustiness

NM not one category

Next step is coupling with risk

management library such as the

ECEL developed by TNO

Sensitivity Analysis (Exposure Algorithm)- One At Time

-80%

-60%

-40%

-20%

0%

20%

40%

60%

80%

100%

-50% -25% -5% Base 5% 25% 50%

% C

han

ge i

n t

he

ou

tpt

con

cen

trat

ion

val

ue

% Input changes

Near field short term (15 min) exposure

cse

tim

bre

rep

totvol

ven

A)

-80%

-60%

-40%

-20%

0%

20%

40%

60%

80%

100%

120%

-50% -25% -5% Base 5% 25% 50%

% C

han

ge i

n t

he

ou

tpt

con

cen

trat

ion

val

ue

% Input changes

Near field long term (8 hoour) exposure

cse

tim

bre

rep

totvol

ven

B)

-80%

-60%

-40%

-20%

0%

20%

40%

60%

80%

100%

120%

-50% -25% -5% Base 5% 25% 50%

% C

han

ge i

n t

he

ou

tpt

con

cen

trat

ion

val

ue

% Input changes

Far field short term (15 min) exposure

cse

tim

bre

rep

totvol

ven

C)

-80%

-60%

-40%

-20%

0%

20%

40%

60%

80%

100%

120%

-50% -25% -5% Base 5% 25% 50%

% C

han

ge i

n t

he

ou

tpt

con

cen

trat

ion

val

ue

% Input changes

Far field long term (8 hour) exposure

cse

tim

bre

rep

totvol

ven

D)

Liguori et al. (in prep.)

Sensitivity Analysis (Exposure Algorithm)- One At Time

Main effects

[NF daily] [FF daily]

CSE 50.9573 49.5076

TIM 42.8422 41.6568

REP 32.5480 31.4588

BRE -27.0343 -26.4670

TOTVOL -32.0269 -31.4291

VEN -50.1953 -49.4954

[NF Acute] [FF Acute]

CSE 89.2789 86.3203

TIM 74.0052 72.8325

REP 65.0045 63.9056

BRE -54.9602 -53.9095

TOTVOL -64.2924 -63.8799

VEN -85.7826 -86.2296

Liguori et al. (in prep.)

CSE Constant Source Emission

TIM Duration of work cycle

BRE Pause between work cycles

REP Frequency - Repetition of the workcycle

TOTVOL Room size

VEN Air Exchange rate

-0.4

-0.2

0.0

0.2

0.4

0.6

0.8

1.0

1.2

30

45

60

75

90

105

120

135

150

165

180

195

210

225

240

255

270

285

300

Room size [m3]

Near field short term (15 min) exposure

-50%

-25%

-5%

5%

25%

50%

Next Step is Performance Assessment and Model Calibration

0

5000

10000

15000

20000

25000

30000

35000

40000

-0.5 0.0 0.5 1.0 1.5 2.0

Time [hours]

FM

PS

pa

rtic

le c

on

cen

trati

on

[n

/cm

3]

NF(FMPS) - BG

C(NF) - Vibration feeder

C(FF) - Laboratory air

FF(FMPS) - BG

5

89

SE3000

Challenge is quality and detail of the case studies for comparison

1. Materials well-characterized

2. Suitable toxicological data on MNM (CMAR)

3. High quality MNM exposure measurement data (personal and

stationary)

THANKS TO MY CO-DEVELOPERS AND TESTERS

Biase Liguori (DTU; NRCWE)

Anne T. Saber (NRCWE)

Ismo K. Koponen (NRCWE)

Steffen F. Hansen (DTU)

Anders Baun (DTU)

Alexander C.Ø. Jensen (DTU; NRCWE)

Håkan Wallin (NRCWE)

Danish Centre for NanoSafety