i. analytical developments cryogenic-free focusing system cryogenic-free chromatography system...
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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
Contributions
• Jacques Hueber• John Ortega• Jan Pollmann• David Tanner
• Pieter Tans
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
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.
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.
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
• 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
Photo: Rick Wunderman, 1997 (Smithsonian Institution www.si.edu)
II. Pico-NARE site
Measurements at Pico:
July 2001 – present:CO, O3, Black Carbon, Meteorology
Aug 2002 – present:NO, NO2, NOy
July 2004 – present:Non-Methane Hydrocarbons
Pico-NARE Atmospheric Observatory
• 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
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)
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
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
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
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
Sampling Sites
Green sites: current stations; blue sites: newly added stations (Nov. 2005)
III. Global Network NMHC Monitoring
Enter keywPrint photo with...1SFP,100C4PPGALL
NMHC-Flask Instrument
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
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
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
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
Ambient & Blank Chromatograms
600 mL
3000 mL
Reference Standard Chromatograms
Cryogenic system
Pico system
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
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
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
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.
-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.
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
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.
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.