Appendix C
Current Sources of Atmospheric and Oceanic Greenhouse Gas Data

ATMOSPHERIC DATA

The atmospheric monitoring sites of Mauna Loa and the South Pole, established during the 1957-1958 International Geophysical Year by C.D. Keeling, have been expanded to both remote and near continental sites (e.g., the ALE/GAGE [Atmospheric Lifetime Experiment-Global Atmospheric Gases Experiment] network, Prinn et al., 1983; the NOAA ESRL [National Oceanic and Atmospheric Administration Earth System Research Laboratory] network, Conway et al., 1994) and to include many other trace gases. The current global greenhouse gas measurement network is an international effort involving about 50 countries. It is coordinated by the World Meteorological Organization’s (WMO’s) Global Atmosphere Watch (GAW) Programme. The NOAA ESRL network, shown in Figure 4.2, is the largest contributing network to GAW. The WMO plays a crucial role in the international monitoring endeavor (1) by promulgating a common calibration scale for each species and quantitative goals for the comparability of measurements by participating laboratories; (2) by promoting comparison programs, measurement system audits, quality assurance and quality control guidelines, and submission of data to the World Data Center for Greenhouse Gases; and (3) by supporting capacity building.

Carbon dioxide (CO2) data are also available from three satellites—SCIAMACHY (Scanning Imaging Absorption Spectrometer for Atmospheric Chartography), AIRS (Atmospheric Infrared Sounder), and IASI (Infrared Atmospheric Sounding Interferometer)— and soon will be available from GOSAT (Greenhouse gases Observing Satellite), the first satellite designed for measuring CO2. A number of studies have used available satellite data to estimate atmospheric CO2 (e.g., Crevoisier et al., 2004, 2009; Buchwitz et al., 2005; Chahine et al., 2005, 2008; Maddy et al., 2008; Schneising et al., 2008; Strow and Hannon, 2008). Table C.1 contains information about the satellites as well as the Orbiting Carbon Observatory (OCO), which failed at launch on February 24, 2009. Unlike AIRS and IASA, OCO and GOSAT had a calibration system in place and a weighting function in the lower troposphere where the signal from surface emissions is strongest. OCO’s spatial resolution was more than an order of magnitude higher than any other satellite’s (instantaneous field of view <3 km2), and its signal-to-noise ratio was three times that of GOSAT.

OCEAN DATA

Carbon Dioxide

The accumulation of anthropogenic CO2 in the ocean resulting from atmospheric uptake can be readily observed. The inventory today is more than 500 billion tons and is increasing at a rate of >1 million tons per hour. Unlike the atmosphere and land surface, the oceanic CO2 signal is not amenable to satellite observation; seawater is a conducting medium and is impervious to electromagnetic radiation. Instead, CO2 is measured during large-scale observing expeditions at approximately decadal intervals. A few time-series stations are also maintained at locations where the changes



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Appendix C Current Sources of Atmospheric and Oceanic Greenhouse Gas Data ATMOSPHERIC DATA gases Observing Satellite), the first satellite designed for measuring CO2. A number of studies have used The atmospheric monitoring sites of Mauna Loa available satellite data to estimate atmospheric CO2 and the South Pole, established during the 1957-1958 (e.g., Crevoisier et al., 2004, 2009; Buchwitz et al., International Geophysical Year by C.D. Keeling, have 2005; Chahine et al., 2005, 2008; Maddy et al., 2008; been expanded to both remote and near continental Schneising et al., 2008; Strow and Hannon, 2008). s ites (e.g., the ALE/GAGE [Atmospheric Life - Table C.1 contains information about the satellites time Experiment-Global Atmospheric Gases Experi- as well as the Orbiting Carbon Observatory (OCO), ment] network, Prinn et al., 1983; the NOAA ESRL which failed at launch on February 24, 2009. Unlike [National Oceanic and Atmospheric Administration AIRS and IASA, OCO and GOSAT had a calibration Earth System Research Laboratory] network, Conway system in place and a weighting function in the lower et al., 1994) and to include many other trace gases. The troposphere where the signal from surface emissions current global greenhouse gas measurement network is is strongest. OCO’s spatial resolution was more than an international effort involving about 50 countries. It an order of magnitude higher than any other satellite’s is coordinated by the World Meteorological Organi- (instantaneous field of view <3 km2), and its signal-to- zation’s (WMO’s) Global Atmosphere Watch (GAW) noise ratio was three times that of GOSAT. Programme. The NOAA ESRL network, shown in Figure 4.2, is the largest contributing network to GAW. OCEAN DATA The WMO plays a crucial role in the international monitoring endeavor (1) by promulgating a common Carbon Dioxide calibration scale for each species and quantitative goals for the comparability of measurements by participating The accumulation of anthropogenic CO2 in the laboratories; (2) by promoting comparison programs, ocean resulting from atmospheric uptake can be read- measurement system audits, quality assurance and qual- ily observed. The inventory today is more than 500 ity control guidelines, and submission of data to the billion tons and is increasing at a rate of >1 million World Data Center for Greenhouse Gases; and (3) by tons per hour. Unlike the atmosphere and land surface, supporting capacity building. the oceanic CO2 signal is not amenable to satellite Carbon dioxide (CO2) data are also available from observation; seawater is a conducting medium and is three satellites—SCIAMACHY (Scanning Imaging impervious to electromagnetic radiation. Instead, CO2 Absorption Spectrometer for Atmospheric Chartogra- is measured during large-scale observing expeditions at phy), AIRS (Atmospheric Infrared Sounder), and IASI approximately decadal intervals. A few time-series sta- (Infrared Atmospheric Sounding Interferometer)— tions are also maintained at locations where the changes and soon will be available from GOSAT (Greenhouse 

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 APPENDIX C TABLE C.1 Specifications of Spaceborne Instruments Capable of Measuring CO2 Specification OCOa GOSATb SCIAMACHYc AIRSd IASIe Tropospheric gases CO2, O2 CO2, CH4, O2, O3, H2O O3, O4, N2O, NO2, CH4, CO, CO2, CH4, O3, CO, CO2, CH4, O3, CO, measured CO2, H2O, SO2, HCHO H2O, SO2 H2O, SO2, N2O CO2 sensitivity Total column including Total column including Total column including near Midtroposphere Midtroposphere near surface near surface surface Horizontal 1.29 × 2.25/5.2 FTS: 10.5/80-790 30 × 60/960 15/1,650 12/2,200 resolution (km)f CO2 uncertainty 1-2 4 14 1.5 2 (ppm)g Instruments 3-channel grating CAI, SWIR/TIR Fourier 8-channel grating Grating spectrometer Fourier transform spectrometer transform spectrometer spectrometer spectrometer Viewing modes Nadir, glint, target Nadir, glint, target Limb, nadir Nadir Nadir Samples per day 500,000 18,700 8,600 2,916,000 1,296,000 Wavelength 0.757-0.772, 1.59- 0.758-0.775, 1.56-1.72, 0.24-0.44, 0.4-1.0, 1.0-1.7, 3.74-4.61, 6.20-8.22, 3.62-5.0, 5.0-8.26, bandpass (µm) 1.62, 2.04-2.08 1.92-2.08, 5.56-14.3 1.94-2.04, 2.265-2.38 8.80-15.4 8.26-15.5 Signal/noise (nadir, >300 @ 1.59-1.62 µm, ~120 @ 1.56-1.72 µm, <100 @ 1.57 µm ~2,000 @ 4.2 µm, ~1,000 @ 12 µm, 5% albedo) >240 @ 2.04-208 µm ~120 @ 1.92-2.08 ~1,400 @ 3.7-13.6 µm, ~500 @ 4.5 µm ~800 @ 13.6-15.4 µm Orbit altitude 705 km 666 km 790 km 705 km 820 km Local time 13:30 ± 0:1.5 13:00 ± 0:15 10:00 13:30 21:30 Revisit time/orbits 16 days/233 orbits 3 days/72 orbits 35 days 16 days/233 orbits 72 days/1,037 orbits Launch date Failed on launch January 2009 March 2002 May 2002 October 2006 Nominal life 2 years 5 years 7+ years 7+ years 5 years NOTES: AIRS = Atmospheric Infrared Sounder; CAI = Cloud and Aerosol Imager; FTS = Fourier transform spectrometer; GOSAT = Greenhouse gases Observing Satellite; IASI = Infrared Atmospheric Sounding Interferometer; OCO = Orbiting Carbon Observatory; SCIAMACHY = Scanning Imaging Absorption Spectrometer for Atmospheric Chartography; SWIR = short-wavelength infrared; TIR = thermal infrared. aCrisp(2008); Crisp et al. (2008). bAkihiko Kuze, Japan Aerospace Exploration Agency, personal communication, 2009; Hamazaki et al. (2007); Shiomi et al. (2007). c; Burrows et al. (1995); Noël et al. (1998); Buchwitz et al. (2005). dAumann et al. (2003); Chahine et al. (2008). ePhulpin et al. (2007); Crevoisier et al. (2009). fInstantaneous field-of-view/Swath. gThe uncertainty represents the estimate of random errors (e.g., the effects of detector noise) and additional systematic errors (e.g., bias caused by cloud and aerosol effects) unaccounted for or otherwise eliminated from the total error. Bias is reduced by successful validation efforts. The GOSAT uncertainty is dominated by the precision (random errors). For OCO, Crisp et al. (2004) and Miller et al. (2007) discuss the observational system simulation experiments, including modeling of the OCO instrument performance characteristics, that led to an instrument design that would meet a measurement requirement of 1 part per million (ppm). The as-built OCO instrument performance was verified during prelaunch tests, which included direct solar observations. The analysis of the latter gave the best confirmation that the as-built instrument performance exceeded its design requirements. The methods for bias reduction and validation are the same for GOSAT and OCO. Washenfelder et al. (2006) demonstrated the OCO validation concept and the essential role of ground-based measurements for meeting those objectives. Bösch et al. (2006) used these ground-based measurements to validate SCIAMACHY CO2. The GOSAT team also plans to use the same validation sites and instruments. OCO planned to include and use Aeronet measure- ments. The OCO validation plan purposely located ground-based validation measurements at Atmospheric Radiation Measurement (ARM) Program sites to capitalize on the wealth of ancillary atmospheric and surface measurements. can be directly measured on shorter time scales. Time anthropogenic CO2 in seawater relied on tracer data, such as bomb 14C. The use of tracers was necessary trends in oceanic CO2 at a single point are illustrated in Figure C.1. Most well-qualified oceanic CO2 datasets because of the high natural background level of dis- reside at the Department of Energy’s Carbon Dioxide solved CO2 in seawater, the complexity of the processes Information Analysis Center.1 affecting its distribution, and the relatively small size Early work to track the accumulated burden of of the anthropogenic signal, all of which combined to make direct observation an uncertain business. Today, there are widely available accurate standards and mea- 1 See .

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 APPENDIX C FIGURE C.1  Time trend of surface water pCO2 offshore Hawaii, showing the direct tracking with atmospheric CO2 forcing and the  resultant change in ocean pH. The change in pH results from reaction with dissolved carbonate ion and causes a decline in the buf- Fig c.1.eps fer capacity of seawater. The penetration to depth can also be seen in the changing subsurface data. SOURCE: Dore et al. (2009).  Copyright 2009 National Academy of Sciences, U.S.A. bitmap image surements, greatly improved knowledge of the func- CO2 burden. An example of the ability to record the tioning of natural cycles, and an enormous increase in increasing storage of anthropogenic CO2 in the ocean the anthropogenic CO2 signal. is shown in Figure C.2. The first demonstrated recovery of the anthropo- genic CO2 signal from direct ocean measurements was Methane by Brewer (1978), who corrected for the subsurface changes in dissolved CO2 due to respiration and car- The chemistry of ocean methane (CH4) is complex bonate dissolution and showed that the residual pCO2 (see the review by Reeburgh, 2007); determining the signal closely resembles the atmospheric CO2 history of extent to which the atmosphere is affected and detecting the water mass. An additional term to correct for local and understanding regional changes (e.g., ocean basin air-sea disequilibrium at the water mass source was scale, or preferably less) are considerable challenges. applied by Gruber et al. (1996), and techniques such First, the global methane budget contains significant as these are widely used today. In addition, compari- oceanic terms (Table C.2). The net ocean emissions to son of datasets from different cruise years now allows the atmosphere are only about 2 percent of the total, simple tracking of the changing ocean anthropogenic mostly because large amounts of methane originating in

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 APPENDIX C emitted from the seafloor, which can affect regional signals, are being updated rapidly. Ocean Water Column. The first ocean water column m easurements of methane were made in the late 1960s (Swinnerton and Linnenbom, 1967), revealing nanomolar concentrations and values well below atmo- spheric equilibrium at depth, indicating oceanic con- sumption within the water column. Measurements of oceanic profiles by Scranton and Brewer (1977) showed the puzzling existence of a significant maximum in FIGURE C.2  Column inventory of anthropogenic CO2 in the  concentration just below the oceanic mixed layer, a pat- ocean as of 1994. The accumulated burden is 388 ± 62 billion  tern later found over large regions of the global ocean tons CO2 and is growing at a rate of ~7.4 billion tons per year.  Thus, the inventory in 2009 is ~500 billion tons CO2. SOURCE:  ( Watanabe et al., 1995). The puzzle was likely solved by Figure 1 from Sabine et al. (2004). Reprinted with permission  Karl et al. (2008), who documented aerobic production from AAAS. of methane by decomposition of methyl phosphonate w hen consumed by phytoplankton in phosphate- starved environments. This process likely accounts for continental margin sediments are consumed by micro- the small net source of CH4 to the atmosphere from the bial processes before they can be released into the fluid upper ocean (Table C.2). Thus, observations of a peak ocean. The terms for methane hydrate decomposition in methane concentrations in the upper ocean should and release and for tracing the signature of gas plumes not be confused with industrial releases. TABLE C.2 Global Net Methane Emissions Emissions Consumption Gross Production Source or Sink (Tg CH4 yr–1) (Tg CH4 yr–1) (Tg CH4 yr–1) Animals 80 0 80 Wetlands 115 27 142 Bogs, tundra (boreal) 35 15 50 Swamps, alluvial 80 12 92 Rice production 100 477 577 Biomass burning 55 0 55 Termites 20 24 44 Landfills 40 22 62 Oceans, freshwaters 10 75.3 85.3 Hydrates 5? 5 10 Coal production 35 0 35 Gas production 40 18 58 Venting, flaring 10 0 10 Distribution leaks 30 18 48 Total sources 500 Chemical destruction –450 Soil consumption –10 40 40 Total sinks –460 688.3 Total production 1,188.3 NOTE: Tg = terragrams = million metric tons SOURCE: Reeburgh (2003).

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 APPENDIX C FIGURE C.3  Acoustic signatures of methane plumes rising from the floor of the Black Sea offshore from the Crimean peninsula.  Fig c.3.eps SOURCE: McGinnis et al. (2006). Copyright 2006 American Geophysical Union. Reproduced by permission of the American Geo- physical Union. bitmap image Black Sea is an unusual case because the deep water Methane in the upper ocean, whether transferred is anoxic and the density contrast between deep and there by exchange with the atmosphere or created surface layers is very strong. Nonetheless, both obser- locally, is consumed through oxidation to CO2 as the vations and models show that even the largest plumes water masses are transferred to depth (Scranton and undergo such significant dissolution during their rise Brewer, 1978). The recent rise in atmospheric CH4 to the surface that only plumes originating from very concentrations is imprinted on this process (Rehder et shallow sources (~100 m depth) can provide a source al., 1999); methane originating in the deep sea around of oceanic CH4 to the atmosphere. vents is also quickly consumed. Satellites. The use of satellites to detect and quantify Venting of Methane from the Seafloor. M ethane is methane releases from the ocean has received little vented naturally from the large reservoirs on the con- attention. The most novel and useful approach was tinental shelves, but little reaches the atmosphere. For taken by MacDonald and colleagues (MacDonald et example, Figure C.3 shows the acoustic detection of al., 2008), who used synthetic aperture radar (SAR) a field of methane plumes rising from the floor of the imagery of the Gulf of Mexico to provide a basin- Black Sea (Schmale et al., 2005; McGinnis et al., 2006). wide inventory of gas seeps based upon their surface Although the height of the plumes (some are higher expression. The team identified some 1,821 sources and than 1,300 m) is impressive, little of the gas is vented to estimated the methane emissions to the atmosphere. the atmosphere. The reason is that gas bubbles venting The effect seen in the SAR imagery (Figure C.4) is the from the seafloor become coated with a film of hydrate damping of capillary waves from the trace oil residue (CH4.6H2O) or oily material from the higher hydro- carried on the rising bubbles and reaching the sea sur- carbons, which slows the dissolution rate of the rising face. A pure methane gas stream with zero associated bubble by about a factor of 4 (Rehder et al., 2002). The

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 APPENDIX C C.2). Although vast quantities of hydrates are known to occur in nature, recent estimates range from 500- 2,500 Gt C (Milkov, 2004) to 63,400 Gt C (Klauda and Sandler, 2005). A map of known hydrate locations is shown in Figure C.5. The potential for global warming to destabilize seafloor methane hydrates has been debated since the early 1980s (e.g., Revelle, 1983). The quantities are so large that destabilization of hydrates could be of grave concern. Fortunately, the danger seems small; almost all of the methane released from seafloor hydrates would simply dissolve into the surrounding water and then be microbially oxidized to CO2 (Hester and Brewer, 2009). FIGURE C.4  SAR  image  of  the  Gulf  of  Mexico  showing  the  Nitrous Oxide surface expression of gas seeps from the trace oil components.  SOURCE: MacDonald et al. (2008). Copyright 2008 American  Fig c.4.eps The oceans are a source of N2O to the atmosphere, Geophysical Union. Reproduced by permission of the American  bitmap image emitting some 25-33 percent of the total flux (Hirsch Geophysical Union. et al., 2006). However, using this information to assign fluxes to any specific region, or decoding the oceanic higher hydrocarbons would not show this effect, but component of trends over reasonable periods of time (a the oil-gas association is very common. decade or so), will be exceptionally difficult. The con- centration of dissolved N2O in seawater is nanomolar. Methane Hydrates. Releases of CH4 from methane The source of N2O in the ocean is intimately hydrates are uncertain (see the question mark in Table FIGURE C.5  Worldwide  map  of  more  than  90  hydrate  occurrences;  such  sites  could  be  monitored  from  space  for  evidence  of  methane releases. SOURCE: Hester and Brewer (2009). Reproduced with permission of Annual Reviews, Inc.; permission conveyed  through Copyright Clearance Center, Inc.

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