Highly time resolved measurements of inorganic gases and aerosols during the

EMEP intensive campaign June 2006

Eiko Nemitz, Rick Thomas, Chiara di Marco, Gavin Phillips: Centre for Ecology and Hydrology (CEH) Edinburgh, UK.

Rami Alfarra, Urs Baltensperger: Paul Scherrer Institute, CH.Rene Otjes, Jan Willem Erisman: Energy Centre of the

Netherlands (ECN), Petten, NL. University of Kopio, FI.

EMEP Intensive Measurement Periods June 2006 / January 2007

• New feature of the new measurement strategy• Also provide an interim solution until EMEP Supersites

(Level 2 & 3) are established• Periods for June 2006 & January 2007 focussing on the

gas / aerosol partitioning of inorganic aerosol• Measurements include

– Daily measurements with manual techniques (Wenche)– Hourly measurements with two different continuous techniques

(this presentation)• So far only preliminary data available from online

techniques

The Aerodyne Aerosol Mass Spectrometer

• Quantitative measurement• Concentration & size distribution• But, limitations:

– Measurement of sub-micron aerosol (100% across 40-600 nm)– Thermal vapourisation at 550°C: non-refractory aerosol only

• Good for: NH4NO3, (NH4)2SO4, NH4Cl, organic aerosol• Does not measure: sea salt, crustal material• Ionisation: Thermal vapourisation, followed by electron

impact ionisation (70 eV)– Less fragmentation than laser ionisation– More fragmentation than chemical ionisation

Particle Inlet (1 atm)

100% transmission (30-600 nm), aerodynamic sizing, linear mass signal.Development of an Aerosol Mass Spectrometer for Size and Composition Analysis of Sub-micron Particles. Jayne et al., Aerosol Science and Technology 33:1-2(49-70), 2000.

QuadrupoleMass Spectrometer

Thermal Vaporization

&Electron Impact

Ionization

Aerodynamic Lens

(2 Torr)

Chopper

Turbo Pump

Turbo Pump

Turbo Pump

TOF Region

Particle Beam Generation Aerodynamic Sizing Particle

Composition

Aerodyne Aerosol Mass Spectrometer (AMS)

• Continuous wet denuder (NH3, HNO3, HCl, SO2, HONO)

• Steam jet aerosol collector (NH4+, NO3

-, SO42-,

Cl-) (MARGA also Na+, K+, Ca2+, Mg2+)• Anions: online anion IC• Cations:

– online cation IC (MARGA) – diffusion membrane / conductivity for NH4

+ (GRAEGOR)

• Two separate sampling boxes for PM2.5 and PM10 (GRAEGOR TSP)

The ECN MARGA/GRAEGOR

The MARGA/GRAEGOR

ICSample

H2O

16.7 l min-1

SJAC Wet Annular Denuder

Liquid feed

valves16.7l min-1

Inlet System

Inlet System

Denudersolution

Liquid level sensors

Peristaltic Pump

Motor

Fan Belt

Steam Generator

Growth & mixing

chamberAir Pump

Aluminum box

SampleBox 2

SampleBox 1

WasteIC

Eluent

De-

gass

er

NH4+

Std (H)

NH4+

Std (L)

Distribution Valves

FIA

H2S

O4

H2O

ICUnit

Flow Meter

NaO

H

NaB

r

FIA Sample

Detector Box

Syringepumps

15 minute delay Loops

IC Pump

Insulation

Insulation & Heating Tape

ICSample

H2O

16.7 l min-1

SJAC Wet Annular Denuder

Liquid feed

valves16.7l min-1

Inlet System

Inlet System

Denudersolution

Liquid level sensors

Peristaltic Pump

Motor

Fan Belt

Steam Generator

Growth & mixing

chamberAir Pump

Aluminum box

SampleBox 2

SampleBox 1

WasteIC

Eluent

De-

gass

er

NH4+

Std (H)

NH4+

Std (L)

Distribution Valves

FIA

H2S

O4

H2O

ICUnit

Flow Meter

NaO

H

NaB

r

FIA Sample

Detector Box

Syringepumps

15 minute delay Loops

IC Pump

Insulation

Insulation & Heating Tape

Comparison AMS vs. MARGA

AMS MARGA/GRAEGOR

Gases No Yes (NH3, HNO3, HCl, SO2,HNO2)

Transmission 40 – 600 nm (~PM1) PM2.5 & PM10/TSP

Sizing Yes No

Aerosol fraction

Non-refractory only: NH4

+, NO3-, SO4

2-, Cl-, OM, H2O

Total: NH4+, NO3

-, SO42-, Cl-

(MARGA only: Na+, K+, Ca2+, Mg2+)

OrganicsAmmoniumNitrateSulphateChlorideNot resolved

1st EMEP Intensive Measurement Period June 2006:Gas / aerosol partitioning of inorganic aerosol

(contributions: ECN, NL; Univ. Kopio, FI; PSI, CH)

Auchencorth, Scotland

Mace Head, Ireland

Payerne, SwitzerlandTotal PM1 = 19.4 g m-3

Total PM1 = 8.6 g m-3

Total PM1 = 6.0 g m-3

Total PM2.5 = 13.7 g m-3

Cabauw, The NetherlandsTotal PM2.5 = > 12.4 g m-3

Harwell, England

Overview of Average Concentrations

Mace Head

AuchencorthPayerne

AuchencorthHarwell

Cabauw

AuchencorthHarwell

Cabauw

Mas

s co

ncen

tratio

n [

g m

-3]

0

5

10

15

20

25

30

NH4+

NO3-

Cl-

SO42-

H2O

Na+

Orgunidentified

NR PM1PM2.5

PM10/TSP

Total Measured Concentrations

50

25

0

Aer

osol

Mas

s [

g m

-3]

1/6 6/6 11/6 16/6 21/6 26/6 1/7

50

25

0

50

25

0

50

25

0

50

25

0

Aerosol M

ass [g m-3]

50

25

0

50

25

0

50

25

0

50

25

0

Mace Head, Ireland

Bush, Scotland

Auchencorth Moss, Scotland (PM2.5)

Cabauw, The Netherlands (PM10)

Payerne, Switzerland

Cabauw, The Netherlands (PM2.5)

Harwell, England (PM2.5)

Auchencorth Moss, Scotland (PM10)

Harwell, England (TSP)

30

20

10

0

1/6 6/6 11/6 16/6 21/6 26/6 1/7

30

20

10

0

Aerosol M

ass [g m-3]

30

20

10

0

30

20

10

0

30

20

10

0

Aer

osol

Mas

s [

g m

-3]

Mace Head, Ireland

Auchencorth, Scotland

Harwell, England

Cabauw, The Netherlands

Payerne, Switzerland

PM 1 (NR) PM 2.5 PM 10

Nitrate

Sulphate30

20

10

0

1/6 6/6 11/6 16/6 21/6 26/6 1/7

30

20

10

0

Aerosol M

ass [g m-3]

30

20

10

0

30

20

10

0

30

20

10

0

Aer

osol

Mas

s [

g m

-3]

Mace Head, Ireland

Auchencorth, Scotland

Harwell, England

Cabauw, The Netherlands

Payerne, Switzerland

PM 1 (NR) PM 2.5 PM 10

Ammonium10

86420

1/6 6/6 11/6 16/6 21/6 26/6 1/7

1086420

Aerosol M

ass [g m-3]

1086420

1086420

1086420

Aer

osol

Mas

s [

g m

-3]

Mace Head, Ireland

Auchencorth, Scotland

Harwell, England

Cabauw, The Netherlands

Payerne, Switzerland

PM 1 (NR) PM 2.5 PM 10

NH3 & SO2

60

40

20

0

1/6 6/6 11/6 16/6 21/6 26/6 1/7

60

40

20

0Con

cent

ratio

n [

g m

-3]

60

40

20

0

Aerosol M

ass [g m-3]

Auchencorth, Scotland

Harwell, England

Cabauw, The Netherlands

NH3 SO2

HNO3 & HCl

10

8

6

4

2

0

1/6 6/6 11/6 16/6 21/6 26/6 1/7

10

8

6

4

2

0Con

cent

ratio

n [

g m

-3]

10

8

6

4

2

0

Aerosol M

ass [g m-3]

Auchencorth, Scotland

Harwell, England

Cabauw, The Netherlands

HNO3 HCl

HNO3 & HONO

10

8

6

4

2

0

1/6 6/6 11/6 16/6 21/6 26/6 1/7

10

8

6

4

2

0Con

cent

ratio

n [

g m

-3]

10

8

6

4

2

0

Aerosol M

ass [g m-3]

Auchencorth, Scotland

Harwell, England

Cabauw, The Netherlands

HNO3 HONO

Data Usage

• Provides powerful dataset for model validation– Bulk concentration– Gas / aerosol partitioning– Fine vs. coarse nitrate– Size distributions

• Data towards aerosol climatology for Europe– Analyse in its own right

• Analysis in local context

Concentration Products[NH3] x [HNO3]

10-6

10-5

10-4

10-3

10-2

10-1

100

[NH

3] x

[HN

O3]

[g

m-3

]

01/06/2006 06/06/2006 11/06/2006 16/06/2006 21/06/2006 26/06/2006 01/07/2006

Harwell Cabauw Auchencorth

Size distribution at CEH EMEP campaign Scottish Site

Average size distributions0.6

0.5

0.4

0.3

0.2

0.1

0.0

-0.1

dM/d

logD

va (µ

g m

-3)

2 3 4 5 6 7 8 9100

2 3 4 5 6 7 8 91000

2

Vacuum Aerodynamic Diameter (nm)

Water Ammonium Nitrate Sulphate Organics

7

6

5

4

3

2

1

0

dM/d

logDva

(µg

m-3

)

2 3 4 5 6 7 8 9100

2 3 4 5 6 7 8 91000

2

Vacuum Aerodynamic Diameter (nm)

Water Ammonium Nitrate Sulphate Organics

8

6

4

2

0

dM/d

logD

va (µ

g m

-3)

2 3 4 5 6 7 8 9100

2 3 4 5 6 7 8 91000

2

Vacuum Aerodynamic Diameter (nm)

Water Ammonium Nitrate Sulphate Chloride Organics PAH

PayerneAuchencorth

Mace Head

Charge Balance (NH4

+ vs. sum of NO3- and SO4

2-)0.12

0.10

0.08

0.06

0.04

0.02

0.00

pred

icte

d N

H4+ =

NO

3- + 2

x S

O42-

[eq

m-3

]

0.120.080.040.00measuredNH4

+ [eq m-3]

Mace Head AMS (NR PM1)

0.5

0.4

0.3

0.2

0.1

0.0

pred

icte

d N

H4+ =

NO

3- + 2

x S

O42-

[eq

m-3

]

0.50.40.30.20.10.0measuredNH4

+ [eq m-3]

Auchencorth AMS (NR PM1)0.30

0.25

0.20

0.15

0.10

0.05

0.00

pred

icte

d N

H4+ =

NO

3- + 2

x S

O42-

[eq

m-3

]

0.300.200.100.00measuredNH4

+ [eq m-3]

Payerne AMS (NR PM1)

0.30

0.25

0.20

0.15

0.10

0.05

0.00

pred

icte

d N

H4+ =

NO

3- + 2

x S

O42-

[eq

m-3

]

0.300.200.100.00measuredNH4

+ [eq m-3]

Cabauw MARGA (NR PM10)

0.5

0.4

0.3

0.2

0.1

0.0

pred

icte

d N

H4+ =

NO

3- + 2

x S

O42-

[eq

m-3

]

0.50.40.30.20.10.0measuredNH4

+ [eq m-3]

Harwell GRAEGOR (NR PM10)

Contribution of Regional Ammonium Aerosols to Exceedances of PM10 Air Quality Standards in Urban Areas

70

60

50

40

30

20

10

0

Aer

osol

Mas

s [

g m

-3]

9-Jun 11-Jun 13-Jun 15-Jun 17-Jun 19-Jun 21-Jun 23-Jun 25-Jun 27-Jun 29-Jun 1-Jul 3-Jul 5-Jul

24-hour Air Quality Standard (PM10)

Annual Mean Air Quality Standard (PM10)

Ammonium Chloride (NR) Nitrate Sulphate Organics PM10 Edinburgh

Concentration StatisticsNH3 HNO3 HCl HONO SO2 NH4

+ NO3- Cl- SO4

2- H2OMace Head 0.39 0.16 0.01 0.81 3.37

0.35 0.09 0.00 0.72 3.090.00 0.01 0.00 0.06 0.001.83 3.62 0.57 2.95 10.10

Auchencorth 1.10 0.14 0.32 0.03 0.42 0.69 0.89 0.77 2.300.36 0.03 0.16 0.01 0.25 0.11 0.21 0.34 1.860.00 0.00 0.05 0.00 0.11 0.00 0.00 0.02 0.41

15.48 1.58 2.74 0.27 4.88 5.48 13.25 6.32 16.10Harwell 2.20 1.03 0.34 0.29 3.04 1.32 3.94 0.80 3.85

2.04 0.59 0.20 0.23 1.39 0.99 2.96 0.26 3.260.54 0.09 0.05 0.04 0.13 0.07 0.15 0.01 0.134.72 7.76 2.67 1.24 60.90 7.32 36.97 8.04 38.20

Cabauw 11.66 1.29 0.86 0.34 2.25 2.39 5.17 0.59 3.119.69 0.66 0.30 0.20 1.50 1.61 3.45 0.24 2.840.82 0.00 0.00 0.04 0.06 0.29 0.00 0.00 0.72

102.11 16.92 9.07 2.75 16.63 14.24 42.66 4.03 8.93Payerne 2.10 1.94 0.03 3.12

1.99 1.56 0.03 2.890.52 0.18 0.00 0.815.20 7.65 0.46 7.74

AerosolsGases

Summary and Outlook• The continuous measurements provide a very nice dataset for

model evaluation• Successful given that this is a new modus operandi, although

more sites would be preferable• For January 2007:

– MARGA at Auchencorth (established supersite)– GRAEGOR at Harwell (supersite being established)– MARGA at Cabauw– AMS at Payerne (?)– Finish AMS at Scandinavian site? (part time?)– German AMS (MPI) at Jungfraujoch– More AMS systems could be deployed (e.g. Univ. Manchester AMSs).

Funding? • Gap in Southern and Eastern Europe• Conflict between long-term research commitments of the

participating institutes