changing distributions of hydrocarbons, alkyl halides, alkyl nitrates, carbon monoxide, and dimethyl...
TRANSCRIPT
Changing Distributions of Hydrocarbons, Alkyl Halides, Alkyl Nitrates,
Carbon Monoxide, and Dimethyl Sulfide during SOFeX
Oliver W. Wingenter1, Karl B. Haase1, Peter Strutton3,2, Gernot Friederich3, Simone Meinardi4, Donald R. Blake4, F. Sherwood Rowland4
1 New Mexico Institute of Mining and Technology, Department of Chemistry2 State University of New York, Stony Brook, Marine Sciences Research Center3 Monterey Bay Aquarium Research Institute4 University of California, Irvine, Department of Chemistry
-169.7 -169.5 -169.3 -169.1-54.5
-54.4
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-54Oxygen (ml/L)
7+6.96 to 76.92 to 6.966.88 to 6.926.84 to 6.886.8 to 6.846.76 to 6.86.72 to 6.766.68 to 6.726.64 to 6.686.6 to 6.646.56 to 6.6
Lat
itu
de
Oxygen (SIO)
-169.7 -169.5 -169.3 -169.1-54.5
-54.4
-54.3
-54.2
-54.1
-54pCO2 (ppm)
353+349.5 to 353346 to 349.5342.5 to 346339 to 342.5335.5 to 339332 to 335.5328.5 to 332325 to 328.5321.5 to 325318 to 321.5314.5 to 318
La
titu
de
Longitude
CO2 (MBARI)
-169.7 -169.5 -169.3 -169.1-54.5
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-54.1
-54 Fluorescence (volts)
15.3+14 to 15.312.7 to 1411.4 to 12.710.1 to 11.48.8 to 10.17.5 to 8.86.2 to 7.54.9 to 6.23.6 to 4.92.3 to 3.61 to 2.3
Lat
itu
de
Fluorescence (SIO)
SOFeX 2002 Observations made on the R/V RevelleSurface Water during the return to the Northern Patch
in patch out of patch % R
compound ave stdeom ave stdeom change O2 CO2 Fluor
O2 (mL/L) 6.90 0.01 6.70 0.02 3 -0.96 0.76
CO2 (ppm) 322.3 0.8 350.0 0.8 -8 -0.84
in patch O2 > 6.87 mL/L
CO2 < 325 ppm
fluor > 10.6 voltsn=11
out of patch O2 > 6.73 mL/L
CO2 < 346 ppm
fluor > 3.75 voltsn=9
12 samples taken on the gradient
Trace Gases Quantified (~50 different species)
Methane and nonmethane-hydrocarbons (over 15 quantified)•Isoprene, ethene, propene, butenes•Ethane, propane, n-butane, n-pentane, n-hexane,
i-butane, i-pentane•Benzene and Ethyne
Alkyl Halides (over 20 quantified)•methyl bromide, methyl iodide, methyl chloride•~20 other halocarbons quantified such as CFCs, HCFCs, HFCs
Alkyl Nitrates•MeONO2, EtONO2, n-PrONO2, i-PrONO2, 2-BuONO2
Carbon Monoxide
DMS, OCS, and CS2
Carbon DioxideOxygen
UCI analytical system
MS
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-54Oxygen (ml/L)
7+6.96 to 76.92 to 6.966.88 to 6.926.84 to 6.886.8 to 6.846.76 to 6.86.72 to 6.766.68 to 6.726.64 to 6.686.6 to 6.646.56 to 6.6
Oxygen (SIO)
-169.7 -169.5 -169.3 -169.1-54.5
-54.4
-54.3
-54.2
-54.1
-54pCO2 (ppm)
353+349.5 to 353346 to 349.5342.5 to 346339 to 342.5335.5 to 339332 to 335.5328.5 to 332325 to 328.5321.5 to 325318 to 321.5314.5 to 318
La
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Longitude
CO2
-169.7 -169.5 -169.3 -169.1-54.5
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-54 Fluorescence (volts)
15.3+14 to 15.312.7 to 1411.4 to 12.710.1 to 11.48.8 to 10.17.5 to 8.86.2 to 7.54.9 to 6.23.6 to 4.92.3 to 3.61 to 2.3
Lat
itu
de
Fluorescence (SIO)
SOFeX 2002 Observations made on the R/V RevelleSurface Water during the return to the Northern Patch
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-54Isoprene (ppt)
460+422 to 460384 to 422346 to 384308 to 346270 to 308232 to 270194 to 232156 to 194118 to 15680 to 11842 to 80
Isoprene
Longitude
Compound
in patch
out of patch % R
ppt ave stdeom SA % ave stdeom SA % change O2 CO2 Fluor
Isoprene 394 13 39300 101 5 10000 290 0.89 -0.93 0.88
Ethene 3001 86 24908 2790 70 23150 7.6 0.48 -0.23 0.08
Propene 1008 29 11100 1000 24 11011 0.8 0.31 -0.23 -0.07
1-Butene 187 5 18600 189 7 18800 -1.1 0.08 0.00 -0.24
i-Butene 758 14 75700 809 17 80800 -6.3 -0.10 0.24 -0.41
t-2-Butene 32 1 3100 32 1 3100 0.0 0.09 0.03 -0.18
c-2-Butene 15.0 0.8 1400. 14.0 0.7 1300 7.1 0.14 -0.10 -0.10
CO (ppb) 214 16 25680 397 17 47837 -46 -0.69 0.83 -0.91
CH4 (ppm) 1.710 0.004 -494 1.705 0.002 -493 0.3 0.47 -0.43 0.39
Gases effecting the oxidative capacity of the atmospheric MBLby consuming hydroxyl, the primary atmospheric oxidant. These
gases also contribute to organic aerosol.
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-54Ethane (ppt)
487.5+475 to 487.5462.5 to 475450 to 462.5437.5 to 450425 to 437.5412.5 to 425400 to 412.5387.5 to 400375 to 387.5362.5 to 375350 to 362.5
La
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Ethane
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-54Propane (ppt)
525+500 to 525475 to 500450 to 475425 to 450400 to 425375 to 400350 to 375325 to 350300 to 325275 to 300250 to 275
Propane
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-54n-Butane (ppt)
110+104 to 11098 to 10492 to 9886 to 9280 to 8674 to 8068 to 7462 to 6856 to 6250 to 5644 to 50
La
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Longitude
n-Butane
SOFeX 2002 Observations made on the R/V RevelleSurface Water during the return to the Northern Patch
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-54n-Pentane (ppt)
222+210 to 222198 to 210186 to 198174 to 186162 to 174150 to 162138 to 150126 to 138114 to 126102 to 11490 to 102
Longitude
n-Pentane
compound in patch out of patch % R
ppt ave stdeom SA % ave stdeom SA % change O2 CO2 Fluor
Ethane 472 7 247 363 7 167 30 0.84 -0.86 0.71
Propane 457 17 3285 301 16 2130 52 0.75 -0.83 0.78
n-Butane 108 11 500 67 8 272 61 0.44 -0.47 0.63
n-Pentane 187 4 18600 108 3 10700 73 0.87 -0.92 0.77
n-Hexane 34 4 3300 22 3 2100 55 0.42 -0.46 0.50
i-Butane 40 6 344 63 9 600 -37 -0.31 0.34 -0.37
i-Pentane 33 5 3150 30 4 2900 8 0.11 -0.08 -0.09
Ethyne 24 1 100 26 1 117 -8 -0.16 0.24 -0.13
Benzene 18 2 338 13 1 225 35 0.36 -0.37 0.39
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-54CH3Br (ppt)
7.6+7.45 to 7.67.3 to 7.457.15 to 7.37 to 7.156.85 to 76.7 to 6.856.55 to 6.76.4 to 6.556.25 to 6.46.1 to 6.255.95 to 6.1
Longitude
Methyl Bromide
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-54CH3Cl (ppt)
536+528 to 536520 to 528512 to 520504 to 512496 to 504488 to 496480 to 488472 to 480464 to 472456 to 464448 to 456
Longitude
Methyl Chloride
Lat
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-54CH3I (ppt)
7.1+6.9 to 7.16.7 to 6.96.5 to 6.76.3 to 6.56.1 to 6.35.9 to 6.15.7 to 5.95.5 to 5.75.3 to 5.55.1 to 5.34.9 to 5.1
Lat
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Longitude
Methyl Iodide
SOFeX 2002 Observations made on the R/V RevelleSurface Water during the return to the Northern Patch
in patch out of patch % R
compound ave Stdeom SA % ave stdeom SA % change O2 CO2 Fluor
CH3Br 7.4 0.2 -1.5 6.4 0.1 -14 14 0.49 -0.61 0.64
CH3I 4.94 0.04 1105 6.4 0.2 1463 -23 -0.82 0.83 -0.63
CH3Cl 472 7 -3.6 459 10 -6.2 2.8 0.04 -0.08 -0.06
CH2Br2 1.09 0.01 20 1.1 0.0 18 1.9 0.08 -0.11 0.01
CHBrCl2 0.140 0.002 17 0.14 0.00 17 0.0 -0.13 0.11 0.04
CH2BrCl 0.35 0.01 63 0.3 0.0 58 3 0.01 -0.03 0.09
CHBr3 1.95 0.03 2.1 1.87 0.07 -2.1 4.3 0.29 -0.23 0.11
CHCl3 6.6 0.1 29 6.8 0.1 33 -2.9 -0.39 0.39 -0.23
CH2Cl2 9.0 0.2 29 10.0 0.2 43 -10 -0.20 0.27 -0.09
C2HCl3 1.3 0.1 915 1.4 0.1 969 -5.0 -0.11 0.12 0.04
C2Cl4 1.4 0.1 109 1.3 0.1 92 9.0 0.00 0.04 0.07
C2H5Cl 2.5 0.1 178 1.9 0.1 111 32 0.43 -0.53 0.50
1,2-C2H4Cl2 1.00 0.03 43 0.90 0.03 29 11 0.20 -0.22 0.29
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-54 C2H5ONO2 (ppt)
10.05+9.8 to 10.059.55 to 9.89.3 to 9.559.05 to 9.38.8 to 9.058.55 to 8.88.3 to 8.558.05 to 8.37.8 to 8.057.55 to 7.87.3 to 7.55
Ethyl Nitrate
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-54CH3ONO2 (ppt)
32.55+31.8 to 32.5531.05 to 31.830.3 to 31.0529.55 to 30.328.8 to 29.5528.05 to 28.827.3 to 28.0526.55 to 27.325.8 to 26.5525.05 to 25.824.3 to 25.05
Lat
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Methyl Nitrate
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-54 i-Propyl Nitrate (ppt)
6.2+6.1 to 6.26 to 6.15.9 to 65.8 to 5.95.7 to 5.85.6 to 5.75.5 to 5.65.4 to 5.55.3 to 5.45.2 to 5.35.1 to 5.2
Lat
itu
de
Longitude
i-Propyl Nitrate
SOFeX 2002 Observations made on the R/V RevelleSurface Water during the return to the Northern Patch
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-542-Butyl Nitrate (ppt)
2.7+2.64 to 2.72.58 to 2.642.52 to 2.582.46 to 2.522.4 to 2.462.34 to 2.42.28 to 2.342.22 to 2.282.16 to 2.222.1 to 2.162.04 to 2.1
Longitude
2-Butyl Nitrate
in patch out of patch % R
compound ave stdeom SA % ave stdeom SA % change O2 CO2 Fluor
MeONO2 26.6 0.5 87 26.4 0.5 86 0.6 0.25 -0.19 -0.18
EtONO2 8.2 0.1 137 8.2 0.1 137 0 -0.06 0.17 -0.42
n-PrONO2 0.64 0.01 191 0.63 0.01 186 2 0.06 0.04 -0.27
i-PrONO2 5.53 0.07 281 5.9 0.1 306 -6 -0.34 0.47 -0.63
2-BuONO2 2.15 0.03 330 2.43 0.04 386 -12 -0.51 0.62 -0.76
Source of NOy to the Atmosphere
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-54OCS (ppt)
1250+1200 to 12501150 to 12001100 to 11501050 to 11001000 to 1050950 to 1000900 to 950850 to 900800 to 850750 to 800700 to 750
Longitude
OCS
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-54DMS (ppt)
9200+8450 to 92007700 to 84506950 to 77006200 to 69505450 to 62004700 to 54503950 to 47003200 to 39502450 to 32001700 to 2450950 to 1700
La
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Longitude
DMS
in patch out of patch % R
compound ave stdeom SA % ave stdeom SA % change O2 Fluor CO2
DMS 7477 420 10736 1561 90 2162 379 0.76 0.89 -0.86
OCS 978 45.9 87 801 22.4 53 22 0.57 0.14 -0.49
CS2 41 0.80 413 42 10.2 425 -2-
0.16 -0.22 0.24
Conclusions•Iron fertilization in the North Patch resulted in large increases in DMS and isoprene. Changes in C2-C4 alkenes were insignificant but may be important as the biomass degrades.
•CO decreased nearly 50 percent. CH4 was unchanged.
•Straight-chain alkanes increased, while branched alkanes increased slightly or were consumed.
•Changes in the oxidative capacity of the atmospheric boundary layer can result in changes in the atmospheric lifetime of DMS. A longer lifetime allows for more transport of this aerosol precursor to the buffer layer. Because the BuL is not directly coupled to the ocean surface, the lifetime of these nascent particles would be considerably longer.
•CH3I was consumed, CH3Br increased while CH3Cl was unchanged.
•Anthropogenic halocarbons such as CFCs were not effected.
AcknowledgmentsKen Johnson and Kevin SullivanDick Barber and Sue Brown and the rest of the Revelle Science TeamCrew of the R/V Revelle