ENVIRONMENTAL LEVELS AND SOURCE … levels and source emissions of ultrafine and nanoparticle size...

$: ENVIRONMENTAL LEVELS AND SOURCE … levels and source emissions of ultrafine and nanoparticle size fractions ... bread baking oven ≥ 640 000.$
ENVIRONMENTAL LEVELS AND SOURCE EMISSIONS OF ULTRAFINE AND

NANOPARTICLE SIZE FRACTIONS

Stefano CERNUSCHIDICA Sezione AmbientalePOLITECNICO DI MILANO

2

Background

UFP - NP• dimensions < 100 nm• base structures for

nanomaterials and nanotechnologiesapplications

S. Cernuschi - Ultrafine and nanoparticles in the atmosphere

3

Background Industrial applications

• electronics (conductive coatings, transistors, semiconductors, photodetectors)• chemical/manufacturing (composite materials, paints, coatings)• medicine and bioapplications (drug delivery, advanced therapies, diagnostics)• energy production (solar cells, batteries, supercapacitors)• sensors/metrology (chemical & physical measurement/monitoring)• environmental technologies (soil remediation, air/water treatment)


4

Background


5

Background


6

Environmental effects


Health hazardsImpacted Particleregion size

Alveolar blood

translocation

Brain bloodnasal translocation

7

Environmental effects


Climatechange

8S. Cernuschi - Ultrafine and nanoparticles in the atmosphere

Characteristics Origin

• primary • secondary gaseous precursors: SO2, NOx, NH3, COV

Size fractions• negligible in terms of mass (conventional measures)• detectable only in terms of number: particle counting (no standard

protocols) Conversion/transformation processes highly active


Characteristics

Modes of urban aerosol Sources Characterization

Nuclei Mode Combustion particles; gas-to-particle conversion

0.001-0.1 μm; high concentration; rapid coagulation; short lifetime

Accumulation Mode

Combustion particles; smog particles; coagulated nuclei-mode particles

0.1-2.5 μm; slow coagulation; long lifetime; accounting for most of visibility effects

Coarse Particle Mode

Windblown dusts; salt particles from sea spray; volcano eruptions; anthropogenic particles from agriculture and surface mining

2.5-100 μm; readily settle down on surface; short lifetime


Characteristics


Sources Natural processes background Additional contribution from human activities main

concerns for• nanotechnologies and nanomaterials• indoor sources• industrial processes involving high temperatures

Recent attention to combustion & industrial emissions• most data available for vehicle exhaust• limited investigations for stationary sources


Measurement challenges General issues

• no standard protocol• significance in terms of number rather than mass• chemical speciation rather troublesome

Source emissions• contribution of condensable fraction from semivolatiles

driven by atmospheric gas dilution• evaluation of condensation effects by diluting and

cooling exhaust gas prior to measurements


Measurement techniquesOptical techniques: CPC (condensation particle counter)

No size distribution evaluation

CPC1. Particle size growing2. Laser optical counting

Sample gas Mixing with additive(alcohol)

Size growing by additive surface condensation

1. Growing

2. Optical counter (laser scattering)


Measurement techniquesInertial impaction: ELPI (electrical low pressure impactor)


Measurement techniquesElectrical mobility: DMA (differential mobility analyzer)


Measurement techniques Aerosol time of flight MS: continuous concentration/size distribution/chemical

speciation


Air concentration levels

PU concentrations in selected environments

10 100 1000 10000 100000 1000000

rural and coastal areas

kitchens

restaurants

public buses

smoking areas

indoor domestic

urban areas

urban traffic sites

10 100 1000 10000 100000 1000000

rural and coastal areas

kitchens

restaurants

public buses

smoking areas

indoor domestic

urban areas

urban traffic sites

Particle number/cm3


Air concentration levelsPU concentrations in selected urban environments

Type of site Typical concentration (particles/cm3)

Natural/rural background(distance relevant sources > 10 km) 2∙103 - 1∙104

Remote urban(distance relevant sources 3-10 km) 5∙103 - 1,5∙104

Urban background(< 2500 veh/h within 50 m) 5∙104 - 7∙104

Urban traffic (roadside) 1,5∙104 - 8,5∙104



PU concentrations in urban areas atroadside locations


Air concentration levels Nucleation event at South Pole


Air concentration levels Nucleation event in urban area


Air concentration levels Urban vs rural – Pianura Padana average daily values


Air concentration levels Urban vs rural – Pianura Padana hourly average values

TR SITE

UB SITE

RU


25

Increase in difference between sites for smaller particle sizes Size distribution for traffic site (TR) affected by “fresh” vehicle emissions:

nucleation mode peak (dp < 30 nm) clearly visible Smaller size fractions affected by local source contributions (traffic), larger

size fractions mainly arising from whole area background levels

Urban vs rural – Pianura Padana average daily size distributions

S. Cernuschi - Ultrafine and nanoparticles in the atmosphere 25


Summer nucleation event

26S. Cernuschi - Ultrafine and nanoparticles in the atmosphere 26


Industrial working levels

Process Concentration within14 - 673 nm size range

(particles/cm³)

Typical size range( nm )

Background, indoor ≥ 10 000

Silica fusion ≥ 100 000 280-520

Metal grinding ≥ 130 000 17-170

Metal soldering ≥ 400 000 36-64

Plasma cutting ≥ 500 000 120-180

Bread baking oven ≥ 640 000 32-109Airport landing runway ≥ 700 000 < 45Electrode welding 54 000 - 3 500 000 33-126

Steel welding 100 000 - 40 000 000 40-600


Indoor residential levels

1E+03

1E+04

1E+05

1E+06

Café Hairdresser Supermarket Church service

Num

ber

conc

entr

atio

n (c

m-3

)

Indoor microenvironments

Home indoor


0.0E+00

5.0E+04

1.0E+05

1.5E+05

2.0E+05

2.5E+05

3.0E+05

4.00

11.50

12.20

12.50

Time

Con

cent

ratio

n (c

m-3

)

0.00 -6.30

6.30-

10.00

10.40 -11.30

11.30 - 13.00

13.00 -14.00

14.00 -15.30

15.30 -18.00

18.00 -19.30

19.30 -

21.00

Home

Home Secondhand smoke

TravelCar

Hairdresser's salon

Travel car

Home Kitchen

Home

21.00 -22.30

22.30-

0.00

Travel car

Home

HomeKitchen

Home

Personal exposures

Saturday

0.0.E+00

5.0.E+04

1.0.E+05

1.5.E+05

2.0.E+05

2.5.E+05

Time

Con

cent

ratio

n (c

m-3

)

00.00 - 07.00

07.00 - 08.30

8.45 - 11.00

11.00 -12.30

12.45 -13.45

14.00 -15.30

15.45 - 16.45

17.00 - 19.00

19.30 - 22.00

22.00 - 00.00

Home

Travel Train

Office

Cafè

Office

TravelSubway & car

Home - Kitchen

Home

Weekday


Personal exposures

Sunday


Source emissionsUP/NP emissions from combustion

Hot flue gas

Primary particles

Condensable particles(semivolatiles nucleation/condensation

driven by atmospheric gas dilutionimmediately at stack discharge)

Cormier et al.,Env. Health Persp. 2006


Sampling/measurement train

2. Controlled dilution with conditioned air

RESIDENCE CHAMBER

DILUTION AIR

DILU

RESIDENCE CHAMBER

DILUTION AIR

DILU

1. Hot sampling +FP capture (≥ 2,5 µm)

GAS IN

CYCLONES

GAS IN

CYCLONES

3. Particle counting(0.007 µm - 10 µm in 12 classes)

Inertial impactor ELPI™

DILUTED GAS

ELPI

DILUTED GAS

ELPIELPIELPI


Heating boilers• advanced wood pellet (150 kWth) with

cyclone for particulate removal• light fuel oil and natural gas boiler

(100 kWth), conventional design• wood log closed fireplace (11 kWth)

Waste to energy (WTE)• 7 plants, capacity 200 - 1200 tpd,

urban/commercial waste• BAT design for flue gas treatment dry removal + SCR (4 plants) dry/wet removal + SCR (2 plants) dry/wet removal + SNCR (1 plant)

Industrial sources• biomass power plant (virgin wood

chops) with SNCR + ESP/FF• regenerative oxidizer for VOCs

removal from thermal soil desorption

Source emissions


Number concentration (particles cm-3)

Wood pellet combustion

5.2E+07

2.9E+04

4.5E+07 3.8E+07

IQR average min max median

Ambient air Dilution sampling

1·108

1·109

1·105

1·104

1·106

1·107

Average = 4,5·107

Part

icle

num

ber

conc

entr

atio

n (c

m-3

)

Background air Low dilution Medium dilution High dilution


Size fractions

Wood pellet combustion

19% 19%28%

74% 73%68%

6% 7% 5%

0%

20%

40%

60%

80%

100%

Size

frac

tion

(%)

0.007<dp<0.05 0.04<dp<0.1 0.1<dp<10

Low dilution Medium dilution High dilution

37 Cernuschi - Ultrafine and nanoparticles in the atmosphere

Closed fireplace

Backgroundair

Lowdilution

Mediumdilution

Highdilution

Hot sampling

Campionamento a caldo Campionamento a freddo

1.5 104

5.1 1076.3 1078.1 107

7.4 1077.8 1076.0 107

A: alta diluzioneM: media diluizioneB: bassa diluizione

1·108

1·109

1·105

1·104

1·106

1·107

1·103

1·102

Average = 6,4·107 Average = 7·107

Part

icle

num

ber

conc

entr

atio

n (c

m-3

)



Size fractions

Closed fireplace

Size

frac

tions

(%)

Backgroundair

Lowdilution

Mediumdilution

Highdilution

Hot sampling


Size distributions

Closed fireplace

0

1

2

3

4

0.01 0.1 1 10Dp [µm]

Hot samplingC = 8.1·107 cm-3

Con

cent

ratio

n(1

0 8 cm

-3)

0

1

2

3

4

0.01 0.1 1 10Dp [µm]

p [

µ] Low dilution

C = 5.6·107 cm-3

Con

cent

ratio

n(1

0 8 cm

-3)

0

1

2

3

4

0.01 0.1 1 10Dp [µm]

High dilutionC = 6.9·107 cm-3

Con

cent

ratio

n(1

0 8 cm

-3)


Dilution ratio

Light fuel oil combustionNumber concentration (particles cm-3)

8.6E+06

2.9E+04

1.3E+06

6.7E+072.2E+07

Ambient air 0 15-20 25-35 40-50

IQR average min max median

Ambient air Dilution samplingHot sampling

1·108

1·109

1·105

1·104

1·106

1·107

Average = 3,3·107

Part

icle

num

ber

conc

entr

atio

n (c

m-3

)


Light fuel oil combustionSize fractions

74%

97% 96%89%

23%

2% 4%10%

3% 1% 0% 1%0%

20%

40%

60%

80%

100%

0 15-20 25-35 40-50

Dilution ratio

Size

frac

tion

(%)

0,007<dp<0,05 0,05<dp<0,1 0,1<dp<10µm


Light fuel oil combustionSize distributions

0.0E+00

1.0E+07

2.0E+07

3.0E+07

4.0E+07

5.0E+07

6.0E+07

7.0E+07

0.01 0.10 1.00 10.00Dp

Low dilutionC = 6.7·107 cm-3

Con

cent

ratio

n (c

m-3

)

0.0E+00

1.0E+07

2.0E+07

3.0E+07

4.0E+07

5.0E+07

6.0E+07

7.0E+07

0.01 0.10 1.00 10.00Dp

High dilutionC = 8.6·106 cm-3

Con

cent

ratio

n (c

m-3

)

0.0E+00

1.0E+07

2.0E+07

3.0E+07

4.0E+07

5.0E+07

6.0E+07

7.0E+07

0.01 0.10 1.00 10.00Dp

Medium dilutionC = 2.2·107 cm-3

Con

cent

ratio

n (c

m-3

)

0.0E+00

1.0E+05

2.0E+05

3.0E+05

4.0E+05

5.0E+05

6.0E+05

7.0E+05

0.01 0.10 1.00 10.00Dp

Con

cent

ratio

n (c

m-3

)

Hot samplingC = 1.3·106 cm-3


WTE - flue gas treatment systems

Dry system

Wet/dry system



WTE - Dry systems

25.695

9.592 9.343 8.04511.798

2.164

< 1.000 < 1.0001.000

10.000

100.000

Background air Hot Low dilution Medium dilution High dilution

TN (

part

icle

s/cm

3 )

IQR mean min max


Size fractions

WTE - Dry systems


Size distributions

WTE - Dry systems

0.0E+00

2.0E+03

4.0E+03

6.0E+03

8.0E+03

1.0E+04

1.2E+04

0.01 0.10 1.00 10.00Dp

Hot samplingC = 3000 cm-3

Con

cent

ratio

n (c

m-3

)

0.0E+00

2.0E+03

4.0E+03

6.0E+03

8.0E+03

1.0E+04

1.2E+04

0.01 0.10 1.00 10.00Dp

Low dilutionC = 10600 cm-3

Con

cent

ratio

n (c

m-3

)

0 55 a t

0.0E+00

2.0E+03

4.0E+03

6.0E+03

8.0E+03

1.0E+04

1.2E+04

0.01 0.10 1.00 10.00Dp

High dilutionC = 17000 cm-3

Con

cent

ratio

n (c

m-3

)

0.0E+00

2.0E+03

4.0E+03

6.0E+03

8.0E+03

1.0E+04

1.2E+04

0.01 0.10 1.00 10.00Dp

Medium dilutionC = 11000 cm-3

Con

cent

ratio

n (c

m-3

)



WTE – Wet/dry systems


Size fractions

WTE – Wet/dry systems


Size distributions

WTE - Wet/dry systems

0.0E+00

1.0E+04

2.0E+04

3.0E+04

4.0E+04

5.0E+04

6.0E+04

0.01 0.10 1.00 10.00Dp

Hot samplingC = 24500 cm-3

Con

cent

ratio

n (c

m-3

)

0.0E+00

1.0E+04

2.0E+04

3.0E+04

4.0E+04

5.0E+04

6.0E+04

0.01 0.10 1.00 10.00Dp

Low dilutionC = 42000 cm-3

Con

cent

ratio

n (c

m-3

)

0.0E+00

1.0E+04

2.0E+04

3.0E+04

4.0E+04

5.0E+04

6.0E+04

0.01 0.10 1.00 10.00Dp

High dilutionC = 70000 cm-3

Con

cent

ratio

n (c

m-3

)

0.0E+00

1.0E+04

2.0E+04

3.0E+04

4.0E+04

5.0E+04

6.0E+04

0.01 0.10 1.00 10.00Dp

Medium dilutionC = 50000 cm-3

Con

cent

ratio

n (c

m-3

)


Fabric filter - removal efficiency

99,00

%

99,03

%

98,85

%

98,54

%

97,21

%

95,14

%

100%

100%

99,98

%

50

60

70

80

90

100

0,01 0,10 1,00 10,00

Diameter (µm)

Part

icle

num

ber

rem

oval

eff

icie

ncy

(%)

Total efficiency• UP+NP (< 100 nm) = 96,8%• FP (100 nm - 1 µm) = 98,9% - >99,9%

Source emissions


LEAP (2011-15)

Comparative assessment

Source emissions EU inventory


IIASA (2013) - Aerosol particle number emissions and size distributions: implementation in the GAINS model and initial results.


Source apportionment Integrated measurements source/atmosphere: comparison with “background”

levels


Source apportionment Integrated measurements source/atmosphere: comparison with “background”

levels 3∙103 - 7∙103

Site A

Site B


Source apportionmentModelling evaluations: source (simulation challenges) or receptor oriented

(emissions chemical speciation requirements)


Source apportionment

WTE ultrafine WTE ultrafine fractionfraction chemicalchemical compositioncomposition

TC: total carbon; ND: unidentified Background airBackground air

Ultrafine Ultrafine fractionfraction chemicalchemical compositioncomposition

TC: total carbon; ND: unidentified

Background airBackground airUltrafine Ultrafine fractionfraction chemicalchemical compositioncomposition




WTE nanoparticle WTE nanoparticle fractionfraction chemicalchemical compositioncomposition


WTE nanoparticle WTE nanoparticle fractionfraction chemicalchemical compositioncomposition



Background air Background air Nanoparticle Nanoparticle fractionfraction chemicalchemical compositioncomposition


Background air Background air Nanoparticle Nanoparticle fractionfraction chemicalchemical compositioncomposition



1E-02

1E-01

1E+00

1E+01

1E+02

1E+03

1E+04

1E+05

1E+06

1E+07

Al As B Ba Cd Co Cr Cu Fe K Mg Mn Mo Na Ni Pb Sb Sr Ti V Zn

Enric

hmen

t fac

tor (

EF)

EF=50

EF=3

Piacenza summer season

ENVIRONMENTAL LEVELS AND SOURCE … levels and source emissions of ultrafine and nanoparticle size...

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Transcript of ENVIRONMENTAL LEVELS AND SOURCE … levels and source emissions of ultrafine and nanoparticle size...