current intercomparison issues - british oceanographic … · current intercomparison issues...
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Current intercomparisonissues
statistics, field studies,
standard comparsions,analytical considerations
Birgit QuackLeibniz-Insitut für Meerswissenschaften Kiel
IFM-GEOMAR
Halocarbon interalibration meeting London 4 February 2008
F irs t name S urname L oc ation6 Katarina Abrahamson S weden1 E lliot Atlas Miami, US AGeorgia Baylis s ‐Brown S OLAS IPO, UE A, UKTom Bell P roject Integrator, UE A, UK
2 Don B lake Irvine C alifornia, US A4 J im Butler NOAA, US A3 Lucy C arpenter Y ork, UK4 Brad Hall NOAA, US A5 C laire Hughes UE A, UK6 Anders Karlsson S wedenC harlotte J ones Y ork, UK
8 Michela Maione Italy9 Manuela Martino UE A, UKMartin Milton National Phys ical L aboratory, UK
10 Bob Moore Dalhous ie, C anada15 P ascal Morin R oscoff, F rance11 Phil Nightingale P lymouth Marine L ab, UK
S imon O'Doherty Bris tol, UK13 Dave Oram UE A, UK14 B irgit Quack IFM‐GEOMAR , Germany15 S tefan R aimund R oscoff, F rance
Heinfried S choler Heidelberg, GermanyDetlef S chulz ‐Bull G ermany
17 Barkley S ive New Hampshire, US A18 Denise S mythe‐Wright S outhampton Oceanography C entre, UK
R oland von G lasow UE A, UKNicola Warwick C ambridge, UK
19 R ay Weiss S an Diego, US A20 J onathan Williams Mainz , Germany21 Y oko Y okouchi J apan
1622
HalocarbonIntercalibration
Meeting
11 countries21 institutions
Medium analyzed bydifferent groups (standards used)
Cryofocussing of air, purge or equilibrator gas,subsequent analytical method
Air+Water Air (g) Water (l)
1 (g+l) 2 5
3 (g) 7 6
4 (g) 8 9
14 (g + l) 13 10
15 (l) 17 11
18(g) 19
21 (g+l) 20
7 7 5total:
GC/MS+GC/ECD GC/MS GC/ECD2 1 (+NCI) 156 3
7 (+NCI) 411 517 818 919 10
13 (+NCI)
142021
7 11 1total:
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C2H3Cl3
32 compoundsfrom 19 reporting groups
in air and water 38(19/19)
13(8/5)
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Mar
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Bob
Moo
re
Phil
Nig
htin
gale
Dav
e O
ram
Birg
it Q
uack
Stef
an R
aim
und
Bar
kley
C.S
ive
Den
yse
Sm
ythe
-Wrig
ht
Ray
Wei
ss
Jona
than
Will
iam
s
Yok
o Yo
kouc
hi
2
2-C3H7I
4(1/3)
0
1
Elli
ot A
tlas
Don
ald
Bla
ke
Lucy
Car
pent
er
Bra
d H
all (
seag
oing
Cla
ire H
ughe
s
And
ers
Kar
lsso
n
Joha
nnes
Lau
be
Mic
hael
a M
alon
e
Man
uela
Mar
tino
Bob
Moo
re
Phil
Nig
htin
gale
Dav
e O
ram
Birg
it Q
uack
Stef
an R
aim
und
Bar
kley
C.S
ive
Den
yse
Sm
ythe
-Wrig
ht
Ray
Wei
ss
Jona
than
Will
iam
s
Yok
o Yo
kouc
hi
2
1-C4H9I + 2-C4H9I
1 (0/1)
0
5
10
15
20
25
30
CH3I CHBr3 CH2Br2 CHBr2Cl CH3Br CHCl3 CH2ClI C2H5I CH3Cl CH2BrI
in totalin airin water
Top 10Groups (19) analyzing halocarbons in air and /or seawater
Primary Standards in use: number refers to institution ( slide 2)
Scott-Marin calibrated with AED against Nist-Hydrocarbon: NCAR-scale : 1, 2, 17, 20
NOAA (inhouse gravimetrical): NOAA-scale : 4, 7, 13,14,18
SIO (inhouse gravimetrical): AGAGE scale : 8,18, 19
Happell (gravimetrcial, 13 years old in Aculife) : 10 (14 CH3I)
Taiyo Nippon Sanso corporation: NIES-scale : 21
(Apel- Riemer Environmental) : 17, 20
for CH3I: NOAA, NCAR ,NIESfor C2Cl4, CHBr3: NOAA
(standard gas from liquid standard) : 3
perm tubes: homemade : 3perm tubes: certified Kintec : 11, 18
gravimetrically prepared liquid standard in MetOH : 1, 5, 6, 9,11
gravimetrically prepared liquid standard in pentane : 14, 22 (other hydrocarbon)
Commercial in MetoH Ultra scientific (100 µg ml-1) : 15,16
Past comparisons
• High points• Low points• Successes• Failures
0
200
400
600
800
1000
1200
0 5 10 15 20 25 30 35 40 45 50
Gas-Ex 98Phase1-04RB-99-06
CHCl3- water equilibrium partial pressuresNOAA cruises and data
latitude
ppt
Mean Min MaxGas-Ex 98 576.6 50.4 7811Phase 1-04 36.9 12.1 63.4RB-99-06 6.7 0.18 33.09
Kiel: Tropical Atlantic (October/November 2002) Kiel: Subtropical North Atlantic (March/April 2004)Kiel: Mauritanian upwelling (March/April 2005)NOAA: Blast 1NOAA: Blast 2NOAA: Blast 3NOAA: Clivar 01NOAA: GasEx 98NOAA: Phase 4-1
CH
2Br 2
[pm
olL-
1 ]
Latitude North [°]
0
1
10
10050
10-80 -70 -60 -50 -40 -30 -20 -10 0 10 20 30 40 50
0
1
10
10050
10-80 -70 -60 -50 -40 -30 -20 -10 0 10 20 30 40 50
Kiel: Tropical Atlantic (October/November 2002) Kiel: Subtropical North Atlantic (March/April 2004)Kiel: Mauritanian upwelling (March/April 2005)NOAA: Blast 1NOAA: Blast 2NOAA: Blast 3NOAA: Clivar 01NOAA: GasEx 98NOAA: Phase 4-1
CH
Br 3
[pm
olL-
1 ]
Latitude North [°]
CHBr3 between NOAA and Kiel Atlantic looks ok!?CH2Br2 data are more consistent
0
1
2
3
4
5
6
7
8
9
Jul 98 Aug 98 Oct 98 Nov 98 Jan 99 Mar 99 Apr 99 Jun 99
Atm
osph
eric
CH
Br 3
(ppt
)
CGO--NOAA
CGO-Carpenter et al(2003),all dataCGO-Carpenter et al(2003),baseline conditions
0
5
10
15
20
25
0.00 0.20 0.40 0.60 0.80 1.00Fraction of year
Atm
osph
eric
CH
Br3
(ppt
)
MHD--NOAA (1998-2006)
MHD-Carpenter et al(2003),Parforce-1999, all data
MHD-Carpenter et al(2003),Parforce-1999, baselineconditions
We did compare in our poster Lucy's data at Mace Head and Cape Grimwith some from NOAA and they seemed OK, but there was no intercalibration.Is that an issue or is it a possible solution to the problem?
0
1
2
3
4
5
6
7
8
9
0 5 10 15 20 25 30 35 40 45 50
CH2Br2-KIELCH2Br2-MIAMICH2Br2-meteor-NCCH2Br2-meteor-NOAACH2Br2-PSE92-YokouchiCH2Br2-Appledore Island-SiveCH2Br2-Oceanographer-93?CH2Br2-XMAS ISLAND GND-UCI/NCCH2Br2-MACE HEAD-PARFORCECH2Br2 -PEM TROPICS B-UCICH2Br2-PEM TROPICS-NCARCH2Br2-MIAMICH2Br2-KIELCH2Br2-GASEX98-AOMLCH2Br2-GASEX98-NCAR
CHBr3 [ppt]
CH2Br2 [ppt]
Compilation of Elliot Atlas
CH
2Br 2
(ppt
v)
1.2
1.4
1.6
1.8
2.0
2.2
2.4
2.6
CH2Br2 Canisters (UNH)CH2Br2 TF GC (UNH)CH2Br2 Canisters (UCI)
CH
Br 3
(ppt
v)
0
2
4
6
8
10
12CHBr3 Cansisters (UNH)CHBr3 TF GC (UNH)CHBr3 Canisters (UCI)
EDT
6/2/04 6/3/04 6/4/04
CH
3I (p
ptv)
0.0
0.2
0.4
0.6
0.8
1.0
1.2 CH3I Canisters (UNH)CH3I TF GC (UNH)CH3I Canisters (UCI)
pre-ICARTT Intercomparison AIRMAP Observing Station at Thompson Farm Durham, NH
10
10/17 (13:00)
10/19 (11:00)
10/25
(11:0
0)
10/29 (23:00)
10/31 (23:00)11/01 (23:00)
11/04
(22:0
0)
11/07 (22:00)
11/11 (10:00)
11/13 (21:00)
Cruise M55 October 12 - November 17. 2002 (Curacao-Douala)with air mass 120hr-backward trajectories
Boreal autumn CHl a (SeaWiFS)
Past direct comparisons high points, low points, successes, failures
Steve Montzka, Elliot Atlas, Jonathan Williams tropical Atlantic October 2002, Meteor 55
0,0
0,5
1,0
1,5
2,0
2,5
3,0
3,5
4,0
4,5
5,0
14.1
0
16.1
0
18.1
0
20.1
0
22.1
0
24.1
0
26.1
0
28.1
0
30.1
0
1.11
3.11
5.11
7.11
9.11
11.1
1
13.1
1
15.1
1
CH2Br2 (NOAA)CH2Br2 (Mainz)CH2Br2 (NCAR)
Atmosphere Atmosphere Atmosphereregular range regular range regular rangeMin Max Mean
Butler, 2002( tropical Atlantik)CH2Br2 0.6 2.61 1.0Atlas, 2002( tropical Atlantik)CH2Br2 0.7 5 1.0
NCARMainzNOAAKiel
Looks good for CH2Br2 .
0,0
0,5
1,0
1,5
2,0
2,5
3,0
3,5
4,0
4,5
5,0
14.1
0
16.1
0
18.1
0
20.1
0
22.1
0
24.1
0
26.1
0
28.1
0
30.1
0
1.11
3.11
5.11
7.11
9.11
11.1
1
13.1
1
15.1
1
C2Cl4 (NOAA)C2Cl4 (Mainz)C2Cl4 (NCAR)
Systematic small offset for C2Cl4, also between Mainz and NCAR , although they use the same scale.
CH3Br CHCl3
0
10
20
30
40
50
60
70
10/1
4
10/1
6
10/1
8
10/2
0
10/2
2
10/2
4
10/2
6
10/2
8
10/3
0
11/1
11/3
11/5
11/7
11/9
11/1
1
11/1
3
11/1
5
NCARMainzNOAA
CH3Br
0
2
4
6
8
10
12
14
10/1
4
10/1
6
10/1
8
10/2
0
10/2
2
10/2
4
10/2
6
10/2
8
10/3
0
11/1
11/3
11/5
11/7
11/9
11/1
1
11/1
3
11/1
5
NCARMainzNOAA
CHCl3
0
1
2
3
4
5
6
7
8
9
10/1
4
10/1
6
10/1
8
10/2
0
10/2
2
10/2
4
10/2
6
10/2
8
10/3
0
11/1
11/3
11/5
11/7
11/9
11/1
1
11/1
3
11/1
5
NCARMainzNOAA-no ppt scale
CH3ICH3I
0
10
20
30
40
50
60
70
80
90
10/1
4
10/1
6
10/1
8
10/2
0
10/2
2
10/2
4
10/2
6
10/2
8
10/3
0
11/1
11/3
11/5
11/7
11/9
11/1
1
11/1
3
11/1
5
NCARMainzNOAA
CH2Cl2CH2Cl2
0
5
10
15
20
25
30
35
4010
/13
10/1
5
10/1
7
10/1
9
10/2
1
10/2
3
10/2
5
10/2
7
10/2
9
10/3
1
11/2
11/4
11/6
11/8
11/1
0
11/1
2
11/1
4
11/1
6
NCARNOAAKiel
CHBr3
Atmosphere Atmosphere Atmosphereregular range regular range regular rangeMin Max Mean
Butler, 2002( tropical Atlantik)CHBr3 0.71 37.23 5.56Atlas, 2002( tropical Atlantik)CHBr3 0.5 27 2.7
Factor of two difference for CHBr3
NCAR1.2Kiel 0.6
0
1
2
3
4
5
6
3/21/05 3/23/05 3/25/05 3/27/05 3/29/05 3/31/05 4/2/05 4/4/05 4/6/05
date
CH
2Br2
[ppt
]MIAMI-CH2Br2Kiel-CH2Br2
Mauritanian UpwellingPoseidon cruise 320/1Atmospheric data
0
2
4
6
8
10
12
14
16
18
20
3/21/05 3/23/05 3/25/05 3/27/05 3/29/05 3/31/05 4/2/05 4/4/05 4/6/05
date
CH
Br3
[ppt
]
MIAMI-CHBr3Kiel-CHBr3
Mauritanian UpwellingPoseidon cruise 320/1Atmospheric data
The systematic calibration offset caused a flux difference:mean CHBr3 flux (Miami-calibration): 1.050 pmol m2 hr-1) mean CHBr3 flux (Kiel-calibration): 2600 pmol m2 hr-1) Quack et al., 2007, in press
Poseidon 320/1 (March /April 2005) cruise track
Again a factor of two calibrationoffset for CHBr3 between Kiel and Miami, now treated as systematic...
Quack, Atlas et al., 2007
0
1
2
3
4
5
6
7
8
9
CH3I CH2Br2 CHBr2Cl CHBr3
ppt
MiamiKiel
CH3I CH2Br2 CHBr2Cl CHBr3Mean RSMAS 2.05 2.43 0.53 6.41STDV 0.73 0.54 0.18 2.57Mean Kiel 1.18 2.24 0.33 3.03STDV 0.39 1.05 0.24 3.20
Intercomparsion of air samples above the Mauritianian upwelling
The systematic calibration offset for CHBr3 caused a flux difference:mean CHBr3 flux (Miami-calibration): 1.050 pmol m2 hr-1) mean CHBr3 flux (Kiel-calibration): 2600 pmol m2 hr-1) Quack, Atlas et al., 2007,
0.26
8.48
24.1
93.4
0.7
0.44
0.11
8.26
25.1
97.5
0.60
0.35
0.27
9.39
25.8
1
89.8
0.84
0.51
0.56
0.55
0
10
20
30
40
50
60
70
80
90
100
CH3I CHCl3 C2H3Cl3 CCl4 CH2Br2 CHBr3
pmol
mol
-1
NOAA 1/1/2004NOAA 8/5/2005Miami 8/2005Kiel 4/2005
Standard /SX3254(Kiel)comparison Miami /NOAA/Kiel
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
CH2Br2 CHBr3
NOAA MiamiKiel
9.40
0.17
24.9
0
7.60
0.63
0.36
10.3
4
0.40
17.0
9
5.24
0.56
3.09
0.33
10.2
6
0.22
22.1
8
10.5
9
1.24
3.55
1.91
0
5
10
15
20
25
30
CH3Br CH3I CH2Cl2 CHCl3 CH2Br2 C2Cl4 CHBr3
NOAA-ESRL MRUEA MRNCAR MR
Standard intercomparsion 2008 Johannes Laube (Universität Frankfurt)pm
ol m
ol-1
other intercomparisons should be available: Weiss, Oram, Sive ?
ICARTT Informal VOC Intercomparison (Subset of 51 gases)Don Blake - UCI
0
5
10
15
20
25
30
35
CHCl3
C2HCl3
C2Cl4
CH3Br
CH3ICH2B
r2
CHBr3MeO
NO2
EtONO2
i-PrO
NO2n-P
rONO2
2-BuO
NO23-P
eONO2
2-PeO
NO2pp
tv
UCIEAUNH
Halocarbons and Alkyl Nitrates
Total ion chromatogramm of sea water
CH3I
CHBr3
CH2Br2
CHBr2Cl
SIM
Halocarbons are in pmol, while hydrocarbons coelute in n-µmol, often yielding thesame fragments (M, M+1 and M-1 at high concentrations): 43(42,44).. +14...85...127,141,.
The liquid gas standard method
21.0
0
42.6
0
95.4
8
1.98 5.
40
5.39
2.10
2.08
2.16
2.10
0.00
0.19
0.19
5.86
0.00
0.07
0.02
0.18
0.00
0.16
0.60
33.6
7
12.3
6
7.49
4.75
1.53
11.5
9
5.40 7.
62
0
10
20
30
40
50
60
70
80
90
100H
FC-1
34a
HC
FC-2
2
CFC
-12
CH
3Cl
CFC
-114
HC
FC-1
42b
H-1
211
CH
3Br
CFC
-11
CFC
-11
HC
FC-1
41b
CH
3I
CFC
-113
CH
2Cl2
CH
Cl3
CH
3CC
l3
CC
l4
CH
2Br2
C2C
l4
CH
Br3
C6H
6
CO
S
HC
FC-2
1
HFC
-152
a
HC
FC-1
24
CH
2BrC
l
C2H
Cl3
CH
BrC
l2
CH
Br2
Cl
Compounds
stan
dard
mix
ing
ratio
[ppt
v]
purported concentrationanalyzed by NOAA [Steve Montzka)
The compounds have been diluted in water in advance, injected in a steel tank via a sixport-valve-loop and then pressurized with Nitrogen.
The liquid gas standard method
20.6
8
41.9
7
94.0
4
1.95 5.
32
5.31
2.08
2.05
2.13
2.07
0.00
0.06
0.12
12.1
7
0.00
0.10
0.07
0.29
0.06 0.71
0.02
36.7
4
12.3
7
7.92
5.20
1.93
12.4
1
3.39
10.9
9
0
10
20
30
40
50
60
70
80
90
100H
FC-1
34a
HC
FC-2
2
CFC
-12
CH
3Cl
CFC
-114
HC
FC-1
42b
H-1
211
CH
3Br
CFC
-11
CFC
-11
HC
FC-1
41b
CH
3I
CFC
-113
CH
2Cl2
CH
Cl3
CH
3CC
l3
CC
l4
CH
2Br2
C2C
l4
CH
Br3
C6H
6
CO
S
HC
FC-2
1
HFC
-152
a
HC
FC-1
24
CH
2BrC
l
C2H
Cl3
CH
BrC
l2
CH
Br2
Cl
Compounds
stan
dard
mix
ing
ratio
[ppt
v]
purported concentrationanalyzed by NOAA [Steve Montzka)
Purported and actual measured compounds and concentrations vary extremst in flask 1.
The liquid gas standard method
21.0
0
42.6
0
95.4
8
1.98 5.
40
5.39
2.10
2.08
2.16
2.10
0.00
0.19
0.19
5.86
0.00
0.07
0.02
0.18
0.00
0.16
0.60
33.6
7
12.3
6
7.49
4.75
1.53
11.5
9
5.40 7.
62
0
10
20
30
40
50
60
70
80
90
100H
FC-1
34a
HC
FC-2
2
CFC
-12
CH
3Cl
CFC
-114
HC
FC-1
42b
H-1
211
CH
3Br
CFC
-11
CFC
-11
HC
FC-1
41b
CH
3I
CFC
-113
CH
2Cl2
CH
Cl3
CH
3CC
l3
CC
l4
CH
2Br2
C2C
l4
CH
Br3
C6H
6
CO
S
HC
FC-2
1
HFC
-152
a
HC
FC-1
24
CH
2BrC
l
C2H
Cl3
CH
BrC
l2
CH
Br2
Cl
Compounds
stan
dard
mix
ing
ratio
[ppt
v]
purported concentrationanalyzed by NOAA [Steve Montzka)
Purported and actual measured compounds and concentrations also show the same differences in flask 2. (Dilution of compounds had been aided in an ultrasonic bath which possibly has destroyed the compounds)
Sample issues
Distribution of e.g. CHBr3 (CH3I) and others in a water sample
CHBr3 CHBr3
CHBr3
CHBr3
CHBr3
CHBr3
CHBr3
CHBr3
CHBr3
CHBr3
CHBr3
CHBr3
CHBr3
CHBr3
CHBr3
CHBr3
CHBr3
CHBr3
CHBr3
CHBr3
CHBr3
CHBr3
CHBr3
CHBr3
CHBr3
CHBr3
CHBr3
CHBr3 CHBr3
CHBr3
CHBr3
CHBr3
CHBr3
CHBr3
CHBr3
CHBr3
CHBr3
CHBr3
CHBr3
CHBr3
CHBr3
CHBr3
CHBr3
CHBr3
CHBr3
CHBr3
CHBr3
Storage is not possible without conservation (anybody tried?)After three days in the refrigerator there were >30% differences
Analytical Concerns
Bromoform is a difficult gas to recover from water samples. Recoveries are influenced by temperature and dessicant used, but also by the composition of the oceanic sample. Optimizing and standardizing techniques would improvecomparison of independent data sets.
Total CHBr3 in a water sample appears distributed among dissolved, adsorbed, and particulate phases.
Theoretical recovery rates based on Moore et al. (1995)
CHBr3 Example
0
10
20
30
40
50
60
70
80
90
100
0 1,000 2,000 3,000 4,000 5,000Purgevolume for 90 ml Sample (ml)
% R
ecov
ery
of C
HBr
3
10°C
20°
30°
40°50°60°70°80°90°
0
5
10
15
20
25
30
35
20.5°N 17.2°W6.9 m
1.6 µg chla/L
19.5°N 16.8°W4.8 m
2.1 µg chla/L
17.5°N 16.5°W14 m
7.8 µg chla/L
19.0°N 18.0°W3.5 m
1.4 µg chla/L
19.0°N 18.0°W3.5 m
1.4 µg chla/Lsonicated
CH
Br3 [
pmol
/L]
0,2 µm-filteredGFF-filteredunfiltered
Sample description
P320/1
0
5
10
15
20
25
30
35
20.5°N 17.2°W6.9 m
1.6 µg chla/L
19.5°N 16.8°W4.8 m
2.1 µg chla/L
17.5°N 16.5°W14 m
7.8 µg chla/L
19.0°N 18.0°W3.5 m
1.4 µg chla/L
19.0°N 18.0°W3.5 m
1.4 µg chla/Lsonicated
CH
Br 3
[pm
ol/L
]
0,2 µm-filteredGFF-filteredunfiltered
The influence of filtration on CHBr3 concentrationsin waters samples of various chl a content.
0
5
10
15
20
25
30
350,
2 µm
-filte
red
0,2
µm-fi
ltere
d
0,2
µm-fi
ltere
d
GFF
-filte
red
GFF
-filte
red
GFF
-filte
red
Hea
dspa
cem
etho
d(8
8ml w
ater
, 412
ml a
ir)
unfil
tere
d
unfil
tere
d
unfil
tere
d
unfil
tere
d
unfil
tere
d
unfil
tere
d_so
nica
ted
unfil
tere
d_so
nica
ted
unfil
tere
d_so
nica
ted
unfil
tere
d_so
nica
ted
Sample 104787: depth 4.83mlat19.5 long -17, 3/26/2007
tota
l
tota
l
tota
l
tota
l
tota
l
Mean 10.1, RSD:15
Different sample treatments
Results of first and second purges after
0
10
20
30
40
50
60
Sample 1 Sample 2 Sample 3 Sample 4
CH
Br3 [
pmol
L-1]
Concentrations of CHBr3
after different analytical treatments of four ocean water samples
cold
-pur
ge70
°C p
urge
GFF
-filte
red
(0.2
bar
)0.
2-fil
tere
d (0
.2 b
ar)
Ultrafiltration(>3.5 bar)
Ultrasonication
unfil
tere
d0.
7 µm
filte
red
0.2
µm fi
ltere
d
200
n m15
0 nm
75 n
m15
nm
Ultr
ason
icat
ion
unfil
tere
d
cold
-pur
ge70
°C p
urge
GFF
-filte
red
(0.2
bar
)0.
2-fil
tere
d (0
.2 b
ar)
Ultt
rafil
tratio
n (>
3.5
bar)
15
n m
Ultr
ason
icat
ion
unfil
tere
d
Ultt
rafil
tratio
n (>
3.5
bar)
15
nm
Ultt
rafil
tratio
n (>
3.5
bar)
15
nm
cold
-pur
ge70
°C p
urge
GFF
-filte
red
(0.2
bar
)0.
2-fil
tere
d (0
.2 b
ar)
cold
-pur
ge70
°C p
urge
GFF
-filte
red
(0.2
bar
)0.
2-fil
tere
d (0
.2 b
ar)
cold-purge
70°C-purge unfiltered
70°C-purge, without POC>0.7µm 70°C-purge,without POC>0.2µmdissolved+DOC+POCcontent>0.2µmdissolved+DOC+POCcontent>0.15µmdissolved+DOC+POCcontent>0.075µmdissolved+DOC+POCcontent > 0.0075µmdissolved+DOC+POC
dissolved+DOC+POC<0.7µm
dissolved+DOC+POC<0.2µm
Practical considerations (some issues from Jim Butler).
What is the most reliable standard?Are perm tubes reliable? (Issues involved, e.g. )Are liquids reliable? (e.g.: degradation, longterm stabitlity)What is the repeatability?Are cylinders reliable? (e.g.: degradation, longterm stabitlity)
Is the analytics firm? (e.g.: coelutions)
Can the data of different analytical methods be compared? ( e.g.:equilibrator, purge and trap)
How does one make a comparison between someone who is using liquid standards and someone who uses cylinders?
How to best intercalibrate between atmospheric and ocean analysis?
Also, how to deal with super-short-lived compounds?
How to deal with compounds that are analyzed differently?
Intercomparison is the short-term answer. Intercalibration, combined withintercomparison is a long-term answer, but in the end, how do we make this happen?