Atmospheric Emissions Of Ethanol From Wineries: Andrew Hart
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Atmospheric Emissions of Ethanol from Wineries Andrew Hart SARP University of California, Irvine Irvine, California 92617
1
Overview
Introduction
Wine Production
Earths Atmosphere VOCs OVOCs Ethanol DMS
Results
Source Sample Ambient Air Measurements Analysis of Ethanol and DMS
2
Composition of the Atmosphere
78% N2
21% O2
0.9% Ar 0.03-0.034% CO2 and other trace gases
3 Fullenberg, G., and A. Wier (2000), The Chemistry of Pollution, John Wiley & Sons Ltd., West Sussex, England.
Altitude (km)
50 40
Stratopause
STRATOSPHERE
30 Tropopause
20 10
TROPOSPHERE 150
200
250
Temperature (K)
300
Stratosphere 15-50 km altitude “Ozone Layer” Temperature inversion: very stable air, little mixing Troposphere Lowest ~18 km of atmosphere Heated by adsorption of solar radiation at surface 4 Weather: clouds, precipitation, turbulent air mixing
Volatile Organic Compounds (VOCs)
Organic compounds that have a high vapor pressure and easily form vapors under ambient conditions
Nonmethane Hydrocarbons (NMHCs) Halocarbons Alkyl Nitrates Oxygenated VOCs (OVOCs) 5
Oxygenated Volatile Organic Compounds (OVOCs)
OVOCs are trace gases that are among the family of organic compounds present in the global atmosphere OVOCs oxidize to form local or regional ozone in the presence of NOx in a catalytic process OVOCs can have both positive and negative affects on air quality
alternative additives for fuel e.g. ethanol toxic to inhalation e.g. acrolein
Koppmann, R., and J. Wildt (1997), Volatile Organic Compounds in the Atompshere, Blackwell Publishing Ltd, Oxford, UK. Harley, R. et al. (1996), Impact of oxygenated gasoline use on California light-duty vehicle emissions, Environ. Sci. Technol., 30, 661–670.
Sources of OVOCs
OVOCs have both primary and secondary sources
e.g. anthropogenic, biogenic, and photooxidation origins
automobile exhaust industrial processes solvent evaporation biomass burning synthesis and emission via plants in the oxidation pathways of other VOCs 7
Koppmann, R., and J. Wildt (1997), Volatile Organic Compounds in the Atompshere, Blackwell Publishing Ltd, Oxford, UK.
Winemaking
Fermentation is initiated by adding the juices and skins together, which contain natural yeasts further producing alcohol and carbon dioxide
Dimethyl sulfide (DMS) is a also known wine constituent that is formed during yeast fermentation and wine aging
Gonzales, A. et al. (2006), Life Cycle Assesment of Wine Production Process. Moreno-Arribas, M., and C. Polo (2008), Wine Chemistry and Biochemistry, Springer , New York.
8
Flight 1
Grid Study
Ethanol (pptv)
Overlay of Flight 1 and Grid Data
9
10
Wineries in California
11
75
50
25
7.2 8.0
100
9.0 10.0 11.0 12.0 13.0 14.0 15.0
-1 16.0 31* - alpha-Pinene (B) - 17.107 32* - 17.198 33* -- n-Propylbenzene m-Ethyltoluene (B)(B) - 17.239
BF7190R
30* - i-Propylbenzene (B) - 16.862
29* - o-Xylene (B) - 16.517
28* - m/p-Xylene (B) - 16.215
27 - 15.294
150
24* - Toluene (B) - 14.841 25* - 2-Methylheptane (B) - 14.943 26* - 3-Methylheptane (B) - 15.096
23 - 14.353
22 - 13.924
19* (B) - (B) 13.502 20* -- 2-Methylhexane 2,3-Dimethylpentane - 13.531 21* - 3-Methylhexane (B) - 13.629
18* - 2,4-Dimethylpentane (B) - 12.906
17 - 12.712
15 - 12.276 16* - n-Hexane (B) - 12.398
14* - 3-Methylpentane (B) - 12.025
13 - 2-Methylpentane (B) - 11.812
10 - 11.455 11.445 11 12 - 11.517
225
8* - 10.871
275
9* - 2,2-Dimethylbutane (B) - 11.103
329 SARPSOURCE #11 [modified by Melissa Yang, 3 peaks manually assigned] mV 4* - Ethanol (B) - 9.351
300
6* - Isoprene (B) - 10.487 7* - 10.604
5* - n-Pentane (B) - 10.328
3* - Methanol (B) - 8.626
2 - 8.175
1* - acetaldehyde (B) - 7.727
Chromatogram of Source Sample Inside a Winery Int_Chan_5
250
~300 ppbv
200
175
DMS= 777 pptv
125
min
12 17.4
Chromatograms of Samples Obtained Nearby Vineyards BF6415 BF7055 BF6307 BF6190 BF7253
5.00
25* - 11.988
23* - 2-Methylpentane (B) - 11.819 24 - 11.884
21* - Cyclopentane (B) - 11.682 22* - 2,3-Dimethylbutane (B) - 11.733
19 - 11.524 20* - 11.581
18 - 11.282
5.50
9 - 9.399
6.00
7* - n-Butane (B) - 7.742
6* - acetaldehyde (B) - 7.650
6.50
8 - Methanol (B) - 8.578
7 ppbv
7.00
16 - 11.051
8.00
13* - n-Pentane (B) - 10.397
11* - i-Pentane (B) - 9.777
8.50
7.50
14 - Isoprene (B) - 10.487
9.00
17 - 2,2-Dimethylbutane (B) - 11.145
9.50
15 - 10.554
10.00
12* - acetone (B) - 9.851
27 ppbv
10.50
Int_Chan_5 Int_Chan_5 Int_Chan_5 Int_Chan_5 Int_Chan_5
10* - Ethanol (B) - 9.485
1 - SARPGRID #23 [modified by Melissa Yang, 3 peaks manually assigned] 2 - SARPGRID #5 [modified by Melissa Yang, 3 peaks manually assigned] 3 - SARPGRID #15 [modified by Melissa Yang, 5 peaks manually assigned] 4 - SARPGRID #42 [modified by Melissa Yang, 3 peaks manually assigned] 11.14 5 - SARPGRID #4 [modified by Melissa Yang, 6 peaks manually assigned] mV
3 4125
4.52 6.91
13 min 7.50
8.00
8.50
9.00
9.50
10.00
10.50
11.00
11.50
12.01
Correlations of Ethanol with DMS
A strong correlation exists between ethanol and DMS when the main source of ethanol is a winery and an anti-correlation 14 is present when the main source is a dairy
Summary
OVOCs, such as ethanol, oxidize to form local or regional ozone in the presence of NOx in a catalytic process A high correlation observed for ethanol and DMS suggests wineries as the main source of emissions of ethanol An anti-correlation observed for ethanol and DMS suggests dairies as the main source
15
Future Goals
Performing a grid study in the Napa Valley area to better understand and determine the influences of wineries on the emission of ethanol in the Central Valley
16
Acknowledgements
Dr. Sherwood Rowland Dr. Don Blake Melissa Yang Rowland/Blake Research Group NASA NSERC
17
Sources: Winery vs. Dairy
18
7.00
6.00
5.00 12
3.7 5.0 6.0 7.0 8.0
9.00
8.00 11* - i-Pentane (B) - 9.777
9.0 10.0 11.0 12.0 13.0 14.0 15.0
4.41 16.0
46* (B) - 17.165 47*--n-Propylbenzene m-Ethyltoluene (B) - 17.231 48 - 1,3,5-Trimethylbenzene (B) - 17.294
BF6415 BF7055
45* - i-Propylbenzene (B) - 16.871
43* 44 -- Styrene o-Xylene(B) (B)- 16.459 - 16.509
42 - 16.081
41* - n-Octane (B) - 15.407
40 - 15.126
39* - Toluene (B) - 14.861
35* - 2,2,4-Trimethylpentane (B) - 13.867 36*--14.057 n-Heptane (B) - 14.002 37* 38 - 14.125
29 - Benzene (B) - 13.248 30 31 -- 13.327 Cyclohexane (B) - 13.399 32*- 2,3-Dimethylpentane - 2-Methylhexane (B) (B) - 13.503 33* - 13.547 34 - 3-Methylhexane (B) - 13.633
27 - 12.283 28* - n-Hexane (B) - 12.389
19 -- 11.524 20* 11.581 21* (B) - 11.682 22* -- Cyclopentane 2,3-Dimethylbutane (B) - 11.733 23* - 2-Methylpentane (B) - 11.819 24 - 11.884 25* - 11.988 26* - 3-Methylpentane (B) - 12.066
16 - 11.051 17 - 2,2-Dimethylbutane (B) - 11.145 18 - 11.282
10.00 12* - acetone (B) - 9.851
12.00 10* - Ethanol (B) - 9.485
1 - SARPGRID #23 [modified by Melissa Yang, 3 peaks manually assigned] 13.08 2 - SARPGRID #5 [modified by Melissa Yang, 3 peaks manually assigned] mV
13* - n-Pentane (B) - 10.397 14 - Isoprene (B) - 10.487 15 - 10.554
9 - 9.399
8 - Methanol (B) - 8.578
6* - acetaldehyde (B) - 7.650 7* - n-Butane (B) - 7.742
5* - i-Butane (B) - 6.623
4* - CH3Cl (B) - 5.973
1 - Propene (B) - 4.529 2 - Propane (B) - 4.670 3 - 4.876
Chromatogram of Samples Nearby Vineyard Int_Chan_5 Int_Chan_5
11.00
19 min 17.4
1
Overview
Introduction
Wine Production
Earths Atmosphere VOCs OVOCs Ethanol DMS
Results
Source Sample Ambient Air Measurements Analysis of Ethanol and DMS
2
Composition of the Atmosphere
78% N2
21% O2
0.9% Ar 0.03-0.034% CO2 and other trace gases
3 Fullenberg, G., and A. Wier (2000), The Chemistry of Pollution, John Wiley & Sons Ltd., West Sussex, England.
Altitude (km)
50 40
Stratopause
STRATOSPHERE
30 Tropopause
20 10
TROPOSPHERE 150
200
250
Temperature (K)
300
Stratosphere 15-50 km altitude “Ozone Layer” Temperature inversion: very stable air, little mixing Troposphere Lowest ~18 km of atmosphere Heated by adsorption of solar radiation at surface 4 Weather: clouds, precipitation, turbulent air mixing
Volatile Organic Compounds (VOCs)
Organic compounds that have a high vapor pressure and easily form vapors under ambient conditions
Nonmethane Hydrocarbons (NMHCs) Halocarbons Alkyl Nitrates Oxygenated VOCs (OVOCs) 5
Oxygenated Volatile Organic Compounds (OVOCs)
OVOCs are trace gases that are among the family of organic compounds present in the global atmosphere OVOCs oxidize to form local or regional ozone in the presence of NOx in a catalytic process OVOCs can have both positive and negative affects on air quality
alternative additives for fuel e.g. ethanol toxic to inhalation e.g. acrolein
Koppmann, R., and J. Wildt (1997), Volatile Organic Compounds in the Atompshere, Blackwell Publishing Ltd, Oxford, UK. Harley, R. et al. (1996), Impact of oxygenated gasoline use on California light-duty vehicle emissions, Environ. Sci. Technol., 30, 661–670.
Sources of OVOCs
OVOCs have both primary and secondary sources
e.g. anthropogenic, biogenic, and photooxidation origins
automobile exhaust industrial processes solvent evaporation biomass burning synthesis and emission via plants in the oxidation pathways of other VOCs 7
Koppmann, R., and J. Wildt (1997), Volatile Organic Compounds in the Atompshere, Blackwell Publishing Ltd, Oxford, UK.
Winemaking
Fermentation is initiated by adding the juices and skins together, which contain natural yeasts further producing alcohol and carbon dioxide
Dimethyl sulfide (DMS) is a also known wine constituent that is formed during yeast fermentation and wine aging
Gonzales, A. et al. (2006), Life Cycle Assesment of Wine Production Process. Moreno-Arribas, M., and C. Polo (2008), Wine Chemistry and Biochemistry, Springer , New York.
8
Flight 1
Grid Study
Ethanol (pptv)
Overlay of Flight 1 and Grid Data
9
10
Wineries in California
11
75
50
25
7.2 8.0
100
9.0 10.0 11.0 12.0 13.0 14.0 15.0
-1 16.0 31* - alpha-Pinene (B) - 17.107 32* - 17.198 33* -- n-Propylbenzene m-Ethyltoluene (B)(B) - 17.239
BF7190R
30* - i-Propylbenzene (B) - 16.862
29* - o-Xylene (B) - 16.517
28* - m/p-Xylene (B) - 16.215
27 - 15.294
150
24* - Toluene (B) - 14.841 25* - 2-Methylheptane (B) - 14.943 26* - 3-Methylheptane (B) - 15.096
23 - 14.353
22 - 13.924
19* (B) - (B) 13.502 20* -- 2-Methylhexane 2,3-Dimethylpentane - 13.531 21* - 3-Methylhexane (B) - 13.629
18* - 2,4-Dimethylpentane (B) - 12.906
17 - 12.712
15 - 12.276 16* - n-Hexane (B) - 12.398
14* - 3-Methylpentane (B) - 12.025
13 - 2-Methylpentane (B) - 11.812
10 - 11.455 11.445 11 12 - 11.517
225
8* - 10.871
275
9* - 2,2-Dimethylbutane (B) - 11.103
329 SARPSOURCE #11 [modified by Melissa Yang, 3 peaks manually assigned] mV 4* - Ethanol (B) - 9.351
300
6* - Isoprene (B) - 10.487 7* - 10.604
5* - n-Pentane (B) - 10.328
3* - Methanol (B) - 8.626
2 - 8.175
1* - acetaldehyde (B) - 7.727
Chromatogram of Source Sample Inside a Winery Int_Chan_5
250
~300 ppbv
200
175
DMS= 777 pptv
125
min
12 17.4
Chromatograms of Samples Obtained Nearby Vineyards BF6415 BF7055 BF6307 BF6190 BF7253
5.00
25* - 11.988
23* - 2-Methylpentane (B) - 11.819 24 - 11.884
21* - Cyclopentane (B) - 11.682 22* - 2,3-Dimethylbutane (B) - 11.733
19 - 11.524 20* - 11.581
18 - 11.282
5.50
9 - 9.399
6.00
7* - n-Butane (B) - 7.742
6* - acetaldehyde (B) - 7.650
6.50
8 - Methanol (B) - 8.578
7 ppbv
7.00
16 - 11.051
8.00
13* - n-Pentane (B) - 10.397
11* - i-Pentane (B) - 9.777
8.50
7.50
14 - Isoprene (B) - 10.487
9.00
17 - 2,2-Dimethylbutane (B) - 11.145
9.50
15 - 10.554
10.00
12* - acetone (B) - 9.851
27 ppbv
10.50
Int_Chan_5 Int_Chan_5 Int_Chan_5 Int_Chan_5 Int_Chan_5
10* - Ethanol (B) - 9.485
1 - SARPGRID #23 [modified by Melissa Yang, 3 peaks manually assigned] 2 - SARPGRID #5 [modified by Melissa Yang, 3 peaks manually assigned] 3 - SARPGRID #15 [modified by Melissa Yang, 5 peaks manually assigned] 4 - SARPGRID #42 [modified by Melissa Yang, 3 peaks manually assigned] 11.14 5 - SARPGRID #4 [modified by Melissa Yang, 6 peaks manually assigned] mV
3 4125
4.52 6.91
13 min 7.50
8.00
8.50
9.00
9.50
10.00
10.50
11.00
11.50
12.01
Correlations of Ethanol with DMS
A strong correlation exists between ethanol and DMS when the main source of ethanol is a winery and an anti-correlation 14 is present when the main source is a dairy
Summary
OVOCs, such as ethanol, oxidize to form local or regional ozone in the presence of NOx in a catalytic process A high correlation observed for ethanol and DMS suggests wineries as the main source of emissions of ethanol An anti-correlation observed for ethanol and DMS suggests dairies as the main source
15
Future Goals
Performing a grid study in the Napa Valley area to better understand and determine the influences of wineries on the emission of ethanol in the Central Valley
16
Acknowledgements
Dr. Sherwood Rowland Dr. Don Blake Melissa Yang Rowland/Blake Research Group NASA NSERC
17
Sources: Winery vs. Dairy
18
7.00
6.00
5.00 12
3.7 5.0 6.0 7.0 8.0
9.00
8.00 11* - i-Pentane (B) - 9.777
9.0 10.0 11.0 12.0 13.0 14.0 15.0
4.41 16.0
46* (B) - 17.165 47*--n-Propylbenzene m-Ethyltoluene (B) - 17.231 48 - 1,3,5-Trimethylbenzene (B) - 17.294
BF6415 BF7055
45* - i-Propylbenzene (B) - 16.871
43* 44 -- Styrene o-Xylene(B) (B)- 16.459 - 16.509
42 - 16.081
41* - n-Octane (B) - 15.407
40 - 15.126
39* - Toluene (B) - 14.861
35* - 2,2,4-Trimethylpentane (B) - 13.867 36*--14.057 n-Heptane (B) - 14.002 37* 38 - 14.125
29 - Benzene (B) - 13.248 30 31 -- 13.327 Cyclohexane (B) - 13.399 32*- 2,3-Dimethylpentane - 2-Methylhexane (B) (B) - 13.503 33* - 13.547 34 - 3-Methylhexane (B) - 13.633
27 - 12.283 28* - n-Hexane (B) - 12.389
19 -- 11.524 20* 11.581 21* (B) - 11.682 22* -- Cyclopentane 2,3-Dimethylbutane (B) - 11.733 23* - 2-Methylpentane (B) - 11.819 24 - 11.884 25* - 11.988 26* - 3-Methylpentane (B) - 12.066
16 - 11.051 17 - 2,2-Dimethylbutane (B) - 11.145 18 - 11.282
10.00 12* - acetone (B) - 9.851
12.00 10* - Ethanol (B) - 9.485
1 - SARPGRID #23 [modified by Melissa Yang, 3 peaks manually assigned] 13.08 2 - SARPGRID #5 [modified by Melissa Yang, 3 peaks manually assigned] mV
13* - n-Pentane (B) - 10.397 14 - Isoprene (B) - 10.487 15 - 10.554
9 - 9.399
8 - Methanol (B) - 8.578
6* - acetaldehyde (B) - 7.650 7* - n-Butane (B) - 7.742
5* - i-Butane (B) - 6.623
4* - CH3Cl (B) - 5.973
1 - Propene (B) - 4.529 2 - Propane (B) - 4.670 3 - 4.876
Chromatogram of Samples Nearby Vineyard Int_Chan_5 Int_Chan_5
11.00
19 min 17.4
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