I. Analytical Developments Cryogenic-Free Focusing System Cryogenic-Free Chromatography System...

34
I. Analytical Developments Cryogenic-Free Focusing System Cryogenic-Free Chromatography System “gas-free” Gas Chromatography Low Power Needs Portable – Modular Instrument Low pptv Detection Limits Detlev Helmig II. Continuous Free Tropospheric Monitoring of NMHC at Pico Mountain, Azores, Portugal III. Global NMHC Monitoring at 25 NOAA Greenhouse Gas Monitoring Network Sites Continuous and Global NMHC Monitoring Research

Transcript of I. Analytical Developments Cryogenic-Free Focusing System Cryogenic-Free Chromatography System...

Page 1: I. Analytical Developments Cryogenic-Free Focusing System Cryogenic-Free Chromatography System gas-free Gas Chromatography Low Power Needs Portable – Modular.

I. Analytical Developments

• Cryogenic-Free Focusing System• Cryogenic-Free Chromatography System• “gas-free” Gas Chromatography• Low Power Needs• Portable – Modular Instrument• Low pptv Detection Limits

Detlev Helmig

II.

Continuous Free Tropospheric Monitoring of NMHC at Pico Mountain, Azores, Portugal

III.

Global NMHC Monitoring at 25 NOAA Greenhouse Gas Monitoring Network Sites

Continuous and Global NMHC Monitoring Research

Page 2: I. Analytical Developments Cryogenic-Free Focusing System Cryogenic-Free Chromatography System gas-free Gas Chromatography Low Power Needs Portable – Modular.

Contributions

• Jacques Hueber• John Ortega• Jan Pollmann• David Tanner

• Pieter Tans

Page 3: I. Analytical Developments Cryogenic-Free Focusing System Cryogenic-Free Chromatography System gas-free Gas Chromatography Low Power Needs Portable – Modular.

Adsorbent materials with their properties: Density: gravimetric density; Surface Area: Surface Area as provided by supplier; net adsorbent mass: mass of individual adsorbent filled into trap for evaluation; Pressure Drop: pressure drop across adsorbent trap filled with adsorbent.

Adsorbent Mesh Size Density Surface Area* Net Adsorbent Mass Pressure Drop Supplierg/cm3 m2/g mg mbar Name, Location, State

Carboxen 1000 60/80 0.52 >1200 56 260 Supelco, Bellefonte, PACarbosieve S III 60/80 0.76 820 64 250 Supelco, Bellefonte, PAMolecular Sieve 5A 40/60 0.89 800 68 120 Alltech, Deerfield, ILMolecular Sieve 4A 40/60 1.07 800 81 130 Alltech, Deerfield, ILSilica Gel 20/45 0.56 750 43 80 Supelco, Bellefonte, PACarboxen 563 20/45 0.55 510 40 70 Sigma-Aldrich, St. Louis, MOActivated Alumina 40/60 1.14 350 86 150 Alltech, Deerfield, ILCarbotrap 20/40 9.20 100 34 § Supelco, Bellefonte, PACarboxen 1016 60/80 0.45 75 44 250 Supelco, Bellefonte, PA* supplier information§ see text

Page 4: I. Analytical Developments Cryogenic-Free Focusing System Cryogenic-Free Chromatography System gas-free Gas Chromatography Low Power Needs Portable – Modular.

Carbosieve S III -10 ºC

0

20

40

60

80

100

120

Re

co

ve

ry (

%)

Eth

ane

1-B

ute

ne

t-2-B

ute

ne

Meth

yl-chlo

ride

n-B

uta

ne

i-B

uta

ne

Pro

pane

Eth

ene

2-M

eth

ylb

ute

ne

2-M

eth

yl-2-b

ute

ne

t-2-P

ente

ne

3-M

eth

yl-1-b

ute

ne

n-P

enta

ne

i-P

enta

ne

c-2

-Bute

ne

2-M

eth

yl-pro

pene

Hexane

3-M

eth

ylp

enta

ne

2-M

eth

ylp

enta

ne

2, 3-D

imeth

ylb

uta

ne

2, 2-D

imeth

ylb

uta

ne

c-2

-Pente

ne

Pro

pene

Acety

lene

Carbosieve S III -30 ºC

0

20

40

60

80

100

120

Re

co

ve

ry (

%)

Eth

ane

1-B

ute

ne

t-2-B

ute

ne

Meth

yl-chlo

rid

e

n-B

uta

ne

i-B

uta

ne

Propane

Eth

ene

2-M

eth

ylb

ute

ne

2-M

eth

yl-2-bute

ne

t-2-P

ente

ne

3-M

eth

yl-1-bute

ne

n-P

enta

ne

i-P

enta

ne

c-2-B

ute

ne

2-M

eth

yl-propene

Hexane

3-M

eth

ylp

enta

ne

2-M

eth

ylp

enta

ne

2, 3-D

imeth

ylb

uta

ne

2, 2-D

imeth

ylb

uta

ne

c-2-P

ente

ne

Propene

Acety

lene

Recovery for target compounds from Carbosieve S III at –10 and –30 ºC. Dark gray section represents the peak area that was found on the microtrap for the respective peak after the first injection, indicating desorption efficiency. Error bars indicate standard deviation for n = 5 injections.

Page 5: I. Analytical Developments Cryogenic-Free Focusing System Cryogenic-Free Chromatography System gas-free Gas Chromatography Low Power Needs Portable – Modular.

three-stage adsorbent trap -30 ºC

0

20

40

60

80

100

120

Re

co

ve

ry (

%)

Eth

ane

1-B

ute

ne

t-2-B

ute

ne

Meth

yl-chlo

ride

n-B

uta

ne

i-B

uta

ne

Pro

pane

Eth

ene

2-M

eth

ylb

ute

ne

2-M

eth

yl-2-b

ute

ne

t-2-P

ente

ne

3-M

eth

yl-1-b

ute

ne

n-P

enta

ne

i-P

enta

ne

c-2

-Bute

ne

2-M

eth

yl-pro

pene

Hexane

3-M

eth

ylp

enta

ne

2-M

eth

ylp

enta

ne

2, 3-D

imeth

ylb

uta

ne

2, 2-D

imeth

ylb

uta

ne

c-2

-Pente

ne

Pro

pene

Acety

lene

Recovery for target compounds from 3-stage adsorbent microtrap (Carboxen 1016, Carboxen 563, Carbosieve S III) at –30 ºC. Dark gray section represents the peak area that was found on the microtrap for the respective peak after the first injection, indicating desorption efficiency. Error bars indicate standard deviation for n = 15 injections.

Page 6: I. Analytical Developments Cryogenic-Free Focusing System Cryogenic-Free Chromatography System gas-free Gas Chromatography Low Power Needs Portable – Modular.

Adsorbent trap schematic. All dimensions are given in millimeters. Figure is not to scale, radial axis is exaggerated. EC = Electrical Connector, RT = Retaining Tube, TC = Thermocouple. RT I.D. = 1.02 mm, trap tube I.D. = 1.83 mm, and trap tube O.D. = 2.11 mm.

filter, 0.25

TC depth, 95

RT, 53

EC, 10

trap tube, 190

teflon tube, 122Carboxen 1016

18Carboxen 563

36Carbosieve SIII

36

RT, 53

TC connector

filter, 0.25

Sample Flow

Desorb Flow

Page 7: I. Analytical Developments Cryogenic-Free Focusing System Cryogenic-Free Chromatography System gas-free Gas Chromatography Low Power Needs Portable – Modular.

• Adsorbent trap assembly schematic. Bottom cover has been moved and front cover has been removed to show detail inside the assembly housing.

peltier coolers

adsorbent trap

copper electrical connector

thermocouple

housing purge

Page 8: I. Analytical Developments Cryogenic-Free Focusing System Cryogenic-Free Chromatography System gas-free Gas Chromatography Low Power Needs Portable – Modular.

Photo: Rick Wunderman, 1997 (Smithsonian Institution www.si.edu)

II. Pico-NARE site

Page 9: I. Analytical Developments Cryogenic-Free Focusing System Cryogenic-Free Chromatography System gas-free Gas Chromatography Low Power Needs Portable – Modular.

Measurements at Pico:

July 2001 – present:CO, O3, Black Carbon, Meteorology

Aug 2002 – present:NO, NO2, NOy

July 2004 – present:Non-Methane Hydrocarbons

Page 10: I. Analytical Developments Cryogenic-Free Focusing System Cryogenic-Free Chromatography System gas-free Gas Chromatography Low Power Needs Portable – Modular.

Pico-NARE Atmospheric Observatory

Page 11: I. Analytical Developments Cryogenic-Free Focusing System Cryogenic-Free Chromatography System gas-free Gas Chromatography Low Power Needs Portable – Modular.

• Portability / Modular / Size

• Limited power

• Cryogen free

• No consumable gasses

• Remote control

• Unattended operation for long periods

• Low free troposphere background concentrations

NMHC Monitoring Challenges

Page 12: I. Analytical Developments Cryogenic-Free Focusing System Cryogenic-Free Chromatography System gas-free Gas Chromatography Low Power Needs Portable – Modular.

ethane

0

1000

2000

3000

Jul-04 Sep-04 Nov-04 Jan-05 Mar-05 May-05 Jul-05 Sep-05

mix

ing

rat

io (

pp

t)

n-propane

0

400

800

1200

Jul-04 Sep-04 Nov-04 Jan-05 Mar-05 May-05 Jul-05 Sep-05

mix

ing

rat

io (

pp

t)

n-butane

0

200

400

600

Jul-04 Sep-04 Nov-04 Jan-05 Mar-05 May-05 Jul-05 Sep-05

mix

ing

rat

io (

pp

t)

Page 13: I. Analytical Developments Cryogenic-Free Focusing System Cryogenic-Free Chromatography System gas-free Gas Chromatography Low Power Needs Portable – Modular.

0

20

40

60

80

100

120

0 500 1000 1500 2000

Number of Samples

Pe

ak

Are

a

ethane

n-propanepropene

1-butene

i-pentane

Sep-05Feb-05 Mar-05 Apr-05 May-05 Jun-05 Jul-05 Aug-05

Pico-GC Calibration Runs

Page 14: I. Analytical Developments Cryogenic-Free Focusing System Cryogenic-Free Chromatography System gas-free Gas Chromatography Low Power Needs Portable – Modular.

NMHC Results from Pico-NARE

1

10

100

1000

10000

3/27 4/3 4/10 4/17 4/24 5/1 5/8 5/15

2005

HC

Mix

ing

Rat

io (

pp

tv)

ethane

propane

n-butane

n-pentane

Page 15: I. Analytical Developments Cryogenic-Free Focusing System Cryogenic-Free Chromatography System gas-free Gas Chromatography Low Power Needs Portable – Modular.

NMHC ratios from Pico-NARE

0

0.05

0.1

0.15

0.2

0.25

0.3

3/26 4/2 4/9 4/16 4/23 4/30 5/7 5/14

[HC

]/[e

tha

ne

]

propane/ethane

butane/ethane4/17 16:00 to4/19 1:00

4/19 17:00 to4/20 15:30

Page 16: I. Analytical Developments Cryogenic-Free Focusing System Cryogenic-Free Chromatography System gas-free Gas Chromatography Low Power Needs Portable – Modular.

NMHC ratios and transport time at the Pico-NARE site

-6

-5

-4

-3

-2

-1

0

-4 -3.5 -3 -2.5 -2 -1.5 -1 -0.5 0

ln(propane/ethane)

ln(b

uta

ne/

eth

ane)

OH only

Mixing and OH

4/17 16:00 to 4/19 1:00

4/19 17:00 to 4/20 15:30

451-500

Mixing Only

Background:ethane=800propane=0butane=0K=0.01 h-1OH=2E6

Starting:ethane:10propane:6butane:4

5d

10d

15d

model:

0

Page 17: I. Analytical Developments Cryogenic-Free Focusing System Cryogenic-Free Chromatography System gas-free Gas Chromatography Low Power Needs Portable – Modular.

Sampling Sites

Green sites: current stations; blue sites: newly added stations (Nov. 2005)

III. Global Network NMHC Monitoring

Page 19: I. Analytical Developments Cryogenic-Free Focusing System Cryogenic-Free Chromatography System gas-free Gas Chromatography Low Power Needs Portable – Modular.

NMHC-Flask Instrument

Page 20: I. Analytical Developments Cryogenic-Free Focusing System Cryogenic-Free Chromatography System gas-free Gas Chromatography Low Power Needs Portable – Modular.

Station/Location

2004 Jan-05 Feb-05 Mar-05 Apr-05 May-05 Jun-05 Jul-05 Aug-05 Sep-05 Oct-05 Nov-05 Dec-05

Amundsen Scott, South Pole 1 1 2 1 4 1 1

Argyle, ME, USA 1

Ascencion, South Atlantic, UK 4 10 8 8 8 4 8 3 3 4 1

Azores, North Atlantic, Portugal 4 3 4 1 2

Baltic Sea, Poland 5 5 2 3

Barrow, AK, USA 1 4 5 2 4 5 3 4 2 1

Black Sea, Romania 3 1 1

Cape Grim, Australia 2 4 3 3 1 3 3 2 4 1

Cold Bay, AK, USA 6 6 7 6 4 4 1 3 2

Crozet, Southern Indian Ocean, France 3 5 5 4 4 3 5 1 1

Guam, South Pacific, USA 1 4 8 4 4 4 9 5 4 6 1

Vestmannaeyar, Iceland 1 2 1

Cape Kumakahi, HI, USA 3 4 4 2 4 3 2 3 2

Mace Head, Ireland 1 3 2 4 3 2 3 2 3

Mauna Loa*, HI, USA (5) (4) (3) (4) (1) (3) (1) (1) (2)

Mt. Waliguam, PR of China+ (1)

Park Falls, WI, USA 1

Samoa, South Pacific+ (1)

Seychelles, Indian Ocean 2 3 5 6 4 1 3 4 3 3

Shemya, Aleution Islands, AK, USA 4 5 4 5 4 1

Souther Great Plains, OK, USA 3 1

Summit, Greenland 9 1 7 3 3 2 5 2 1

Tierra del Fuego, Argentina 1 1 1

Trinidad Head, CA, USA 1 3 5 4 4 2 2 2 4

Wendover, UT, USA 2 2

Zeppelin, Arctiv Ocean, Norway 1 1*contaminated sampler+no regular station

Number of Samples

NMHC Stations and Available Data

Page 21: I. Analytical Developments Cryogenic-Free Focusing System Cryogenic-Free Chromatography System gas-free Gas Chromatography Low Power Needs Portable – Modular.

Summit 2004 - 2005

0

500

1000

1500

2000

2500

3000

3500

20-S

ep

20-O

ct

19-N

ov

19-D

ec

18-J

an

17-F

eb

19-M

ar

18-A

pr

18-M

ay

17-J

un

17-J

ul

16-A

ug

15-S

ep

mix

ing

rat

io (

pp

tV)

ethane

propane

Page 22: I. Analytical Developments Cryogenic-Free Focusing System Cryogenic-Free Chromatography System gas-free Gas Chromatography Low Power Needs Portable – Modular.

Summit 2004-2005

0

50

100

150

200

250

300

20-S

ep

20-O

ct

19-N

ov

19-D

ec

18-J

an

17-F

eb

19-M

ar

18-A

pr

18-M

ay

17-J

un

17-J

ul

16-A

ug

15-S

ep

Mix

ing

Rat

io (

pp

tV)

ethene

propene

i-butane

n-butane

i-pentane

n-pentane

hexane

Page 23: I. Analytical Developments Cryogenic-Free Focusing System Cryogenic-Free Chromatography System gas-free Gas Chromatography Low Power Needs Portable – Modular.
Page 24: I. Analytical Developments Cryogenic-Free Focusing System Cryogenic-Free Chromatography System gas-free Gas Chromatography Low Power Needs Portable – Modular.

Summit 2004-2005

0

100

200

300

400

500

600

700

20-S

ep

20-O

ct

19-N

ov

19-D

ec

18-J

an

17-F

eb

19-M

ar

18-A

pr

18-M

ay

17-J

un

17-J

ul

16-A

ug

15-S

ep

Mix

ing

Rat

io (

pp

tV)

methyl-chloride

Page 25: I. Analytical Developments Cryogenic-Free Focusing System Cryogenic-Free Chromatography System gas-free Gas Chromatography Low Power Needs Portable – Modular.

Ambient & Blank Chromatograms

600 mL

3000 mL

Page 26: I. Analytical Developments Cryogenic-Free Focusing System Cryogenic-Free Chromatography System gas-free Gas Chromatography Low Power Needs Portable – Modular.

Reference Standard Chromatograms

Cryogenic system

Pico system

Page 27: I. Analytical Developments Cryogenic-Free Focusing System Cryogenic-Free Chromatography System gas-free Gas Chromatography Low Power Needs Portable – Modular.

Gas Chromatography System for the Automated, Unattended, and Cryogen-1 Free Monitoring of C2 to C6 Non-Methane Hydrocarbons in the Remote 2

Troposphere 3 4 5

David Tanner (1), Detlev Helmig (1,2*), Jacques Hueber (1), and Paul Goldan(3) 6 (1)Institute of Arctic and Alpine Research, University of Colorado at Boulder, Boulder, CO 7

80309-0450, USA 8 (2) Department of Atmospheric and Oceanic Sciences (ATOC), University of Colorado at 9

Boulder, Boulder, CO 80309-0311, USA 10 (3)Aeronomy Laboratory, National Oceanic and Atmospheric Administration, 325 Broadway, 11

Boulder, CO 80303, USA 12 13 14

*corresponding author, e-mail [email protected] 15 16 17

Manuscript submitted to 18 Journal of Chromatography A 19

20 Revised Version 21

22 January 18, 2005 23

Page 28: I. Analytical Developments Cryogenic-Free Focusing System Cryogenic-Free Chromatography System gas-free Gas Chromatography Low Power Needs Portable – Modular.

CompoundR.F. (PA/vol)/ppb R.F. (%)

RSDD.L. (ppt)600 mL sample

D.L. (ppt)3000 mL sample

Ethane 0.0367 5 60

Propane 0.0590 5 156 31

Propene 0.0672 5 53 11

i-Butane 0.0725 5 6.9 1.4

n-Butane 0.0634 5 7.9 1.6

1-Butene 0.0530 10 9.4 1.9

i-Pentane 0.0619 6 8.1 1.6

n-Pentane 0.0560 6 8.9 1.8

Pico GC NMHC Detection Limits

Page 29: I. Analytical Developments Cryogenic-Free Focusing System Cryogenic-Free Chromatography System gas-free Gas Chromatography Low Power Needs Portable – Modular.

Schematic of the trapping and GC system with components for sample collection. V1 = 4-Port Valco Valve, V2 = 4-Port Valco Valve, V3 = 6-Port Valco Valve, SO1 through SO5 = KIP solenoid shut-off valves, P1 through P6 = Medo compressors and vacuum pumps, MFC1 through 3 = Mass Flow Controllers, GC = Gas Chromatograph, FID = Flame Ionization Detector, Al/KCl PLOT = Al/KCl PLOT column, Cat = Zero Air Catalyst, Vol = 1 L buffer volume, R1 = 5 L min-1 rotometer, R2 and R3 = 0.5 L min-1 rotometer, Std 1 and 2 = Reference Standards 1 and 2, NV = Needle Valve, Blank = Blank Air Flow, Dry Purge = Water Trap Dry Purge Flow, H2O Trap = Water Trap, O3 Trap = Ozone Trap, Ads Trap = Adsorbent Focusing Trap, Pres Sens = Pressure Sensor, H2 Gen = Hydrogen Generator, Scrub = Hydrocarbon Scrubber, Oxygen Scrubber, and Indicating Oxygen Scrubber. Tubing that is connected to the adsorbent trap while it is in the isolated mode has been highlighted.

Ads Trap

H2O Trap

A

V1A

V2B

V3

Std1

Std2

O3 Trap

P1

H2 Gen

P2 P3 P4 P5

P6

MFC2

MFC3

MFC1

Cat

GC

Al/KClPLOT

FID

SO1

SO2

SO3

SO4

SO5

Outlet

PresSens

Blank

Dry Prg

NV

SplgLine

Scrub

Inlet

R1

R2 R3 Vol

H2toFID

Page 30: I. Analytical Developments Cryogenic-Free Focusing System Cryogenic-Free Chromatography System gas-free Gas Chromatography Low Power Needs Portable – Modular.

0

50

100

150

200

250

300

350

-80 -60 -40 -20 0 20 40 60 80

distance from center of trap (mm)

tem

pe

ratu

re (

C)

adsorbent bed

section cooled by copper blockEC EC

Temperature gradient in the adsorbent trap during heating as a function of the distance from the center of the trap. EC = Electrical Connector.

Page 31: I. Analytical Developments Cryogenic-Free Focusing System Cryogenic-Free Chromatography System gas-free Gas Chromatography Low Power Needs Portable – Modular.

-50

0

50

100

150

200

250

300

350

0 10 20 30 40 50 60 70 80 90

time (s)

tra

p t

em

pe

ratu

re (

C)

flash heatinject

bakeout

Temperature of the adsorbent trap as a function of time with the flash heat (12 s), inject (12 s) and bakeout (60 s) periods labeled.

Page 32: I. Analytical Developments Cryogenic-Free Focusing System Cryogenic-Free Chromatography System gas-free Gas Chromatography Low Power Needs Portable – Modular.

Junge Jobson plots (Seychelles)

y = 1.1421x-0.3875

R2 = 0.9338

0.1

1

1 10 100 1000Lifetime (days)

Var

iab

ilit

y (S

ln(x

))

i-Butane

n-Butane

CH3ClEthane

EtheneHexane

i-Pentane

n-PentanePropane

Page 33: I. Analytical Developments Cryogenic-Free Focusing System Cryogenic-Free Chromatography System gas-free Gas Chromatography Low Power Needs Portable – Modular.

0

10

20

30

40

50

60

70

80

90

100

ethane propane n-butane n-pentane propene 1-butene 2-methyl-2-butene

Re

lati

ve

Re

sp

on

se

(%

)

270 C

290 C

300 C

310 C

320 C

Analyte recovery as a function of increasing desorption temperature.

Page 34: I. Analytical Developments Cryogenic-Free Focusing System Cryogenic-Free Chromatography System gas-free Gas Chromatography Low Power Needs Portable – Modular.

0

100

200

300

400

500

0 600 1200 1800 2400 3000

Sampling Volume (mL)

Pea

k A

rea

ethane

propane

propene

n-butane

1-butene

n-pentane

Peak areas resulting from increasing sampling volumes of the breathing air standard.