Atmospheric methane and ethane:

35 years of global monitoring and

15 years of regional measurements
Prof. Donald R. Blake
Department of Chemistry
University of California, Irvine
Irvine, CA 92697-2025
drblake@uci.edu
SARP
June 17, 2015
Barnett Shale,
Texas (33N)

Rarotonga (21S)

Alberta oil sands (57N)

Why do/did we study methane?

Sherry Rowland said to

Why do/did we study methane?

Long-term data are
required to understand
the big picture. Climate
changes over decadal
time scales, so it
requires observations
over the same time
scale. Its critical for
understanding whether
our science is correct
and whether policy
changes are correct.
- Ken Jucks, NASAs upper
atmosphere research
program manager, on the
UC Irvine global
monitoring network

1. CH4 impacts air quality

O2 RO
2

VOCs

NO
RO

OH
HO2

NO2

VOCs

O3

O2

Oxygenated VOCs
VOCs
NOx
SO2

O + O2

VOCs
NOx

Secondary organic aerosol (SOA)

Volatile Organic Compound
(VOC) reactions lead to:
Tropospheric ozone (O3)
Secondary organic aerosol (SOA)

These products impact:

Air quality, global climate

After: www.chem.wisc.edu/users/keutch/ and

www.york.ac.uk/inst/sci/APS/backgrd_files/figure4.gif

CH4 is the leading source of

global tropospheric O3

Tropospheric Chemistry Brief Overview

OH

O2

O2

RO2

RO

HO2 + R=O

H2O
O2

NO

O(1D)

NO2

h
O2

O2

O3

O(3P)

Tropospheric Chemistry Brief Overview

OH

O2

O2

RO2

RO

HO2 + R=O

H2O
O2

NO

O(1D)

NO2

h
O2

O2

O3

O(3P)

2. CH4 contributes to climate change

Source: IPCC 2007 WG1-AR4

LOSU = Level of scientific understanding

The paleoclimatological CH4 record

Current levels of CH4 are
unprecedented in the
paleoclimatological record
(>400,000 yrs)
Pre-industrial CH4 levels:
300-800 ppb
Global CH4 level in 2012:
1807.5 0.7 ppb (UCI)
1808.9
(NOAA)
1808.3
(AGAGE)

Graph: Hansen, Climate Change, 68 (2005)

UCI = University of California, Irvine
NOAA = National Oceanic and Atmospheric Administration
AGAGE = Advanced Global Atmospheric Gases Experiment

Global CH4 measurements since 1978

UC Irvines global CH4 measurements begin in 1978,
when ice core records (polar latitudes only) leave off

IPCC 2007 WG1-AR4

Global CH4 monitoring by UC Irvine

Since 1978 we have
collected >7500 surface
whole air samples in the
remote Pacific, which
have been analyzed for
CH4 and other trace gases

Air sampling in New Zealand

First latitudinal sampling, January 1978

Moderate-lifetime compounds
(CO, ethane, etc)

~ 6-18 months

Ozone

~ 1-2 months

Very-short-lived compounds
(Biogenics, long-chained NMHCs)

Very Long-lived compounds (CO2,

methane, CFCs, etc.)

Stratosphere

Tropopause

Troposphere

Boundary Layer

Stratosphere

Tropopause

Troposphere

Boundary Layer

Laboratory analysis at UC Irvine

CH4 is analyzed using Gas
Chromatography (GC) with
Flame Ionization Detection
Precision: 0.1% (approx. 1.8 ppbv)
Accuracy: 1% (approx. 18 ppbv)

Multi-column GC for other

trace gases (e.g. ethane):
UC Irvines multi-column analytical system

Flame Ionization Detection (FID)

Electron Capture Detection (ECD)
Mass Spectrometer Detection (MSD)

Speciated measurements of C1-C10 VOCs

Alkanes

Alkenes

Aromatics

1. Methane
2. Ethane
3. Propane
4. i-Butane
5. n-Butane
6. i-Pentane
7. n-Pentane
8. n-Hexane
9. n-Heptane
10. n-Octane
11. n-Nonane
12. n-Decane
13. 2,2-Dimethylbutane
14. 2,3-Dimethylbutane
15. 2-Methylpentane
16. 3-Methylpentane
17. 2-Methylhexane
18. 3-Methylhexane
19. 2,3-Dimethylpentane
20. 2,2,4-Trimethylpentane
21. 2,3,4-Trimethylpentane
22. 2-Methylheptane
23. 3-Methylheptane

25. Ethene
26. Propene
27. 1-Butene
28. i-Butene
29. cis-2-Butene
30. trans-2-Butene
31. 1,3-Butadiene
32. 1-Pentene
33. cis-2-Pentene
34. trans-2-Pentene
35. 2-Methyl-1-Butene
36. 2-Methyl-2-Butene
37. 3-Methyl-1-Butene
38. 2-Methyl-1-Pentene
39. 4-Methyl-1-Pentene
40. Isoprene
41. -Pinene
42. -Pinene

51. Benzene
52. Toluene
53. Ethylbenzene
54. m-Xylene
55. o-Xylene
56. p-Xylene
57. Styrene
58. i-Propylbenzene
59. n-Propylbenzene
60. 2-Ethyltoluene
61. 3-Ethyltoluene
62. 4-Ethyltoluene
63. 1,2,3-Trimethylbenzene
64. 1,2,4-Trimethylbenzene
65. 1,3,5-Trimethylbenzene

Alkynes
24. Ethyne

Alkyl Nitrates
43. MeONO2
44. EtONO2
45. i-PrONO2
46. n-PrONO2
47. 2-BuONO2
48. 2-PeONO2
49. 3-PeONO2
50. 3-Methyl-2-BuONO2

Cycloalkanes/-enes
66. Cyclopentane
67. Methylcyclopentane
68. Cyclohexane
69. Methylcyclohexane
70. Cyclopentene

Sulfur Species
71. OCS
72. DMS
73. CS2

Halocarbons
74. CFC-11
75. CFC-12
76. CFC-113
77. CFC-114
78. CCl4
79. CH3CCl3
80. HCFC-22
81. HCFC-124
82. HCFC-141b
83. HCFC-142b
84. HFC-134a
85. HFC-152a
86. H-1211

87. H-1301
88. H-2402
89. CH3Cl
90. CH3Br
91. CH3I
92. CH2Cl2
93. CHCl3
94. CHBr3
95. C2Cl4
96. CHBrCl2
97. CHBr2Cl
98. Ethylchloride
99. 1,2-DCE

Good agreement between UCI and NOAA

Global

UC Irvine perspective:
Our Pacific-based measurements
realistically approximate the global
ethane mixing ratio

NOAA/INSTAAR perspective:
The globally-based NOAA/INSTAAR
measurements realistically
approximate UCIs program
Zonal

Simpson et al., Nature, 2012

Global CH4 levels: Seasonal

Spatial trends:
Strong latitudinal
gradient
More CH4 sources
in N. Hemisphere

Temporal trends:
Strong seasonal cycle
Interannual variations
Long-term increase

The hydroxyl radical (OH) is methanes primary sink

Global CH4 levels: Annual

Global CH4 mixing ratio:
Increase of 185 ppbv (11%)
in the past 30 years

1983: 1622.2 0.6 ppbv

2012: 1807.5 0.7 ppbv

Global CH4 growth:

Slowing growth in the 1980s
with renewed increase since
2007

The global CH4 growth rate was calculated based on

a linear fit to globally averaged mixing ratios
calculated for a given year (one average per year).
The uncertainty is the standard error of the slope.

1983-1994: 11.5 0.6 ppbv yr-1

1995-2006: 2.5 0.4 ppbv yr-1
2007-2012: 5.2 0.5 ppbv yr-1

What drives changes in CH4 growth?

Global CH4 mixing ratio

Global CH4 growth rate

Two elements to methanes global growth rate:

- Long-term growth rate decline (slowing growth)
- Short-term growth rate anomalies (fluctuations)

Why?

Global sources of CH4

Anthropogenic sources (70%)

Fossil fuel*
Ruminant animals
Rice agriculture
Landfills
Biomass burning*

100 Tg CH4 yr-1

80 Tg CH4 yr-1
60 Tg CH4 yr-1
60 Tg CH4 yr-1
50 Tg CH4 yr-1

Natural sources (30%)

Wetlands

Termites
Geological
Hydrates
Oceans
Wildfires
Vegetation

100 Tg CH4 yr-1

20 Tg CH4 yr-1
10 Tg CH4 yr-1
5 Tg CH4 yr-1
4 Tg CH4 yr-1
2 Tg CH4 yr-1
? Tg CH4 yr-1

* Fossil fuel includes coal, oil, gas

* CH4 is also emitted by biofuel (e.g., charcoal, dung)

Denman et al. (2007) (IPCC, Ch. 7); Piccot et al,. JGR, 1996

Global sources of ethane

Anthropogenic sources
Fossil fuel
Biofuel
Biomass burning

8.0-9.2 Tg yr-1
2.6 Tg yr-1
2.4-2.8 Tg yr-1

Minor sources
Oceans
Vegetation

0-0.3 Tg yr-1
Negligible

Stein and Rudolph (2007); Xiao et al. (2008); Pozzer et al. (2010)

Ethane has a fairly simple

source budget
Ethanes major sources are
shared with methane

Concentration

Methane

Ethane

Time

Concentration

Use ethane to understand methane

Methane
Ethane

Time

Methane-only sources:

Ethane & methane sources:

Wetlands
Ruminants

Fossil fuel
Biomass burning, biofuel

Rice paddies
Landfills

Comparison of global ethane and methane

The global ethane mixing ratio and global CH4 growth rate
show a remarkably strong correlation over the past 25+ years.
Using C2Cl4 we have shown that this is source-driven.
Simpson et al., Nature, 2012

Short-term CH4 fluctuations

Wetlands and biomass burning
have contributed to shortterm CH4 fluctuations
1998 anomaly:
- Wetlands and biomass burning
Dlugokencky et al. (2001); Simpson et al. (2006)

2002-2003 anomaly:
- Strong biomass burning influence
Simpson et al. (2006)

Recent anomalies:
- Wetlands
Dlugokencky et al. (2009)

Influence of ENSO
El Nio: Influence on biomass burning
Simpson et al. (2006)

La Nia: Influence on wetlands

ENSO = El Nio Southern Oscillation

Dlugokencky et al. (2009)

Long-term CH4 growth rate decline

If biomass burning and wetlands have influenced
methanes short-term fluctuations, what has caused
the long-term decline in methanes global growth rate?

Simpson et al., Nature, 2012

Dueling methane papers in 2011

Kai et al., Nature (2011):

Aydin et al., Nature (2011):
- Technique: Methane-to-ethane ratio
- Results: Team Fossil Fuel
A decline in the fossil-fuel source of
methane probably caused the late 20th
century slow-down in CH4 growth

- Technique: Methane isotopes

- Results: Team Rice Paddy
Reduced agricultural or other microbial
sources in the Northern Hemisphere
13C observations exclude reduced fossil fuel
emissions as sole cause of CH4 slowdown

Use ethane to understand methane

Similar pattern to CH4
Spatial trends:
Strong latitudinal gradient
More ethane sources
in N. Hemisphere

Temporal trends:
Strong seasonal cycle
Interannual variations
Long-term decrease
(whereas for CH4 recall that
even though its growth rate is
decreasing, its concentration
is still increasing)
Simpson et al., Nature, 2012

1. Declining global ethane levels

Ethane: annual

Global ethane levels:

Decrease of 165 pptv (21%!)
in the past 25 years

1986: 791 19 pptv

2010: 625 12 pptv

Global ethane emissions:

Decrease of 3.0 0.4 Tg yr-1
in the past 25 years
1986: 14.3 Tg yr-1
2010: 11.3 Tg yr-1

1. Net ethane decrease in 25 years= 3.0 0.4 Tg yr-1

For details see Simpson et al., Nature, 2012

2. Ethanes decline driven by fossil fuel

2. Based on modeling studies, we attribute ethanes longterm decrease to a decreasing fossil fuel source

For details see Simpson et al., Nature, 2012

3. Adjust for other ethane sources

3.0 Tg yr-1 = +0.26 + +0.59 + (3.8) Tg yr-1
From 19852010 ethanes three major sources changed as follows:
1. Biomass burning:
2. Biofuel:

3. Fossil fuel:

+0.26 Tg yr-1
+0.59 Tg yr-1

+0.85 Tg yr-1

3.8 Tg yr-1 (3.4 to 4.2 Tg yr-1)

3. Net ethane decrease from fossil fuel

is 3.4 to 4.2 Tg yr-1 (19852010)
For details see Simpson et al., Nature, 2012

4. Relate ethane to methane

For shared sources such as biomass burning and fossil fuel,
ethane and methane are released in characteristic ratios,
quantified by the methane-to-ethane ratio (MER)*
The larger the MER, the more methane is released relative to ethane

* MERs can be mass-based or molar-based.

The above MERs are mass-based.

Jones et al., 2000; Xiao et al., 2008; Katzenstein et al., 2003

4. Relate ethane to methane

For shared sources such as biomass burning and fossil fuel,
ethane and methane are released in characteristic ratios,
quantified by the methane-to-ethane ratio (MER)
The larger the MER, the more methane is released relative to ethane

Use MER = 35 for natural gas in oil fields

Sources of long-term CH4 decline

1. Ethane decline from fossil fuel: 3.4 to 4.2 Tg ethane yr-1
2. MER of natural gas in oil fields: 35 g CH4 / g ethane
3. CH4 decline from fossil fuel (19852010):
3.4 to 4.2 Tg ethane yr-1 35 = 10 to 21 Tg CH4 yr-1
4. By comparison, the total decline in global CH4 emissions
(19852010) is approx. 30 Tg CH4 yr-1
Fossil fuel accounts for at least
3070% of the long-term decline
in global CH4 emissions since the
1980s, significantly contributing
to methanes slowing growth
Simpson et al., Nature, 2012

Regional CH4 and ethane measurements

1. Oil sands bitumen
Mining/upgrading/refining (Alberta)
2008 (ARCTAS), 2010, 2012

Simpson et al., 2010, 2013

2. Oil and natural gas (O&NG)

O&NG fields + other sources (CA, CO, TX, OK, KS)
2007/8 (Mt. Wilson), 2010-14 (SARP), 2013 (Bakersfield)
2002 (TX/OK/KS)
Katzenstein et al., 2003
2012 (DC3), 2013 (SEAC4RS), 2014 (DISCOVER-AQ/FRAPP)

Deepwater Horizon oil spill (Gulf of Mexico)

2010

de Gouw et al., 2011; etc.

3. Shale gas
Barnett Shale + other sources (Texas)
2013

North American fossil fuel signatures

Composition of hydrocarbon sources, 1987

Hydrocarbon components for natural gas, landfills,
feedlots/dairies, sewers and geological seepage

Storage tank hydrocarbon composition

Methane
Ethane
Ethene
Ethyne
Propene
Propane
CH3Cl
i-Butane
n-Butane
i-Pentane
n-Pentane
Benzene
Toluene
Hexane
Heptane

% Downwind
% from
Storage Tank Literature **
69.2*
62.9
10.9
14.6
0.0
0.0
0.0
10.0
10.3
0.0
1.2
1.2
5.1
8.2
1.1
0.5
1.8
0.6
0.0
0.1
0.5
0.7
0.2

* Subtracted 1.81 ppmv Methane Background Concentration

** Berger and Anderson, Modern Petroleum (1992)

U.S. city study: August 1999

4500
Chicago
Houston
New York
Oklahoma City
San Diego
Salt Lake City

4000
3500
3000
2500
2000
1500
1000
500

Toluene

Benzene

Hexane

Isoprene

n-Pentane

Hydrocarbon

i-Pentane

n-Butane

i-Butane

Propene

Propane

Ethyne

Ethene

Ethane

CO

0
CH4

Mixing Ratio (pptv, CH4 &

CO in ppbv)

August 1999 Comparison

Hydrocarbon
Toluene

6000

Benzene

8000

Hexane

Isoprene

n-Pentane

i-Pentane

n-Butane

i-Butane

Propene

Propane

Ethyne

Ethene

Ethane

CO

CH4

Mixing Ratio (pptv, CH4 &

CO in ppbv)

Oklahoma City by season (1999-2000)

Oklahoma City by Season (1999-2000)

10000

August
November
February
May

4000

2000

Southeast U.S. study: April-May 2002

Ground-based grid study

Latitude

Whole air sampling

April 28 May 3, 2002
n = 261

Longitude

Katzenstein et al., PNAS, 2003

Alkanes in the southwestern US: 2002

Surface study
April-May 2002
n = 261

Results
Extensive regional
light hydrocarbon
pollution
Attributed to emissions
from the oil & natural
gas industry
(conventional)
Total U.S. natural gas
emissions underestimated

- n-Butane is a tracer of oil and gas activity

- Ethyne is a combustion tracer

Katzenstein et al., PNAS, 2003

Quick VOC emission estimates

Assumptions
1.
2.

3.

Volume of 720 km x 820 km x 1 km

Ventilation time of 2-3 days
(15 km/hr wind)
No vertical ventilation

Oklahoma and Kansas VOC emissions*

EPA estimate
130 tons/day
Our estimate**
1000-1500 tons/day
* Does not include methane and ethane
** Includes parts of Texas

Growth of hydrofracking in the US

U.S. domestic crude oil production by source, 1990-2040

Permits issued for fracking in Ohio

(Utica Shale) and Pennsylvania
(Marcellus Shale), 2007-2012
Ohio Dept. of Natural Resources and
Pennsylvania Dept. of Environmental
Protection
http://www.eia.gov/forecasts/aeo/er/images/figure_1es-lg.png

Alkanes in the southwestern US: 2012

2012

2002 (CH4)

Airborne study (DC3)

June 30, 2012
Texas and Oklahoma

Results
The 2012 study area was
relatively emission-rich
compared to 2002
However the number of
US gas wells has also
steadily increased from
2002-2012
Miller et al. (2013) also
report that CH4 emissions
have increased and are
much larger than model
and EPA values

Should we redo the experiment to see if we

were wrong in 2002 or if things have changed
Assumptions
1.
2.

3.

Volume of 720 km x 820 km x 1 km

Ventilation time of 2-3 days
(15 km/hr wind)
No vertical ventilation

Oklahoma and Kansas VOC emissions*

EPA estimate
130 tons/day
Our estimate**
1000-1500 tons/day
* Does not include methane and ethane
** Includes parts of Texas

Summary: Regional mass-based MERs

Source
Oil fields
O&NG
O&NG (airborne)
O&NG (ground)
Los Angeles
Los Angeles
Dairy/mix
Dairy

Mission
SARP 2012
DC3 2012
Bakersfield
Bakersfield
ARCTAS-B
Mt. Wilson
Bakersfield
SARP 2012

MER
5.4 1.4
4.4 0.2
15 2
81 2
24 1
24
122 26
286 15

R2
0.44
0.66
0.31
0.99
0.88

0.80
0.98

Take-home message: Methane and ethane sources are often

co-located and Methane-to-Ethane Ratios (MERs) can vary considerably
even within the same source, or depending on how dry the natural gas is.
We recommend using caution when applying these ratios.

Conclusions: Global CH4 and ethane

Ethane
Long-term decline of 21% in 25 yrs caused
by fossil fuel emissions reducions
Short-term peaks linked to biomass burning

Methane
Long-term slowing growth most likely
caused by fossil fuel and not rice paddies
Short-term anomalies mostly related to
wetlands but sometimes to biomass burning

Conclusions: Regional CH4 and ethane

UCI has studied VOC emissions from
oil and natural gas sources since 1999
Mass balance calculations confirmed
oil and natural gas emissions in the
OK/TX region higher than predicted
Comparison with literature and
models points to significantly
increasing emissions from oil and
natural gas sources over time

Well pad, Barnett Shale, Texas

Acknowledgments

Jasons thesis defense photo

Liquefied Petroleum Gas (LPG)

Composition of unburned LPG fuel*
Gas
Median %
Methane
5.6
Ethane
0.19
Propane
25.1
n-Butane
46.1
i-Butane
22.6
n-Pentane
0.03
i-Pentane
0.36

Average %
2.1
0.09
28.4
46.5
22.5
0.03
0.33

*Based on the analysis of 15 LPG-fueled

taxis in Hong Kong (2012-2013) molar %