Agricultural opportunities to mitigate greenhouse gas emissions

Agriculture is a source for three primary greenhouse gases (GHGs): CO(2), CH(4), and N(2)O. It can also be a sink for CO(2) through C sequestration into biomass products and soil organic matter. We summarized the literature on GHG emissions and C sequestration, providing a perspective on how agriculture can reduce its GHG burden and how it can help to mitigate GHG emissions through conservation measures. Impacts of agricultural practices and systems on GHG emission are reviewed and potential trade-offs among potential mitigation options are discussed. Conservation practices that help prevent soil erosion, may also sequester soil C and enhance CH(4) consumption. Managing N to match crop needs can reduce N(2)O emission and avoid adverse impacts on water quality. Manipulating animal diet and manure management can reduce CH(4) and N(2)O emission from animal agriculture. All segments of agriculture have management options that can reduce agriculture's environmental footprint.     

Determining seasonal greenhouse gas emissions from ground-level area sources in a dairy operation in central Texas

Greenhouse gas (GHG) emissions from agricultural production operations are recognized as an important air quality issue. A new technique following the U.S. Environmental Protection Agency Method TO-14A was used to measure GHG emissions from ground-level area sources (GLAS) in a free-stall dairy operation in central Texas. The objective of this study was to quantify and report GHG emission rates (ERs) from the dairy during the summer and winter using this protocol. A weeklong sampling was performed during each season. A total of 75 and 66 chromatograms of air samples were acquired from six delineated GLAS (loafing pen, walkway, barn, silage pile, settling basin, and lagoon) of the same dairy during summer and winter, respectively. Three primary GHGs--methane (CH4), carbon dioxide (CO2), and nitrous oxide (N2O)--were identified from the dairy operation during the sampling periods. The estimated overall ERs for CH4, CO2, and N2O during the summer for this dairy were 274, 6005, and 7.96 g head(-1)day(-1), respectively. During the winter, the estimated overall CH4, CO2, and N2O ERs were 52, 7471, and 3.59 g head(-1)day(-1), respectively. The overall CH4 and N2O ERs during the summer were approximately 5.3 and 2.2 times higher than those in the winter for the free-stall dairy. These seasonal variations were likely due to fluctuations in ambient temperature, dairy manure loading rates, and manure microbial activity of GLAS. The annualized ERs for CH4, CO2, and N2O for this dairy were estimated to be 181, 6612, and 6.13 g head(-1)day(-1), respectively. Total GHG emissions calculated for this dairy with 500 cows were 2250 t of carbon dioxide equivalent (CO2e) per year.     

Greenhouse gas emissions from Canadian peat extraction, 1990-2000: a life-cycle analysis

This study uses life-cycle analysis to examine the net greenhouse gas (GHG) emissions from the Canadian peat industry for the period 1990-2000. GHG exchange is estimated for land-use change, peat extraction and processing, transport to market, and the in situ decomposition of extracted peat. The estimates, based on an additive GHG accounting model, show that the peat extraction life cycle emitted 0.54 x 10(6) t of GHG in 1990, increasing to 0.89 x 10(6) t in 2000 (expressed as CO2 equivalents using a 100-y time horizon). Peat decomposition associated with end use was the largest source of GHGs, comprising 71% of total emissions during this 11-y period. Land use change resulted in a switch of the peatlands from a GHG sink to a source and contributed an additional 15%. Peat transportation was responsible for 10% of total GHG emissions, and extraction and processing contributed 4%. It would take approximately 2000 y to restore the carbon pool to its original size if peatland restoration is successful and the cutover peatland once again becomes a net carbon sink.     

Models to predict emissions of health-damaging pollutants and global warming contributions of residential fuel/stove combinations in China

Residential energy use in developing countries has traditionally been associated with combustion devices of poor energy efficiency, which have been shown to produce substantial health-damaging pollution, contributing significantly to the global burden of disease, and greenhouse gas (GHG) emissions. Precision of these estimates in China has been hampered by limited data on stove use and fuel consumption in residences. In addition limited information is available on variability of emissions of pollutants from different stove/fuel combinations in typical use, as measurement of emission factors requires measurement of multiple chemical species in complex burn cycle tests. Such measurements are too costly and time consuming for application in conjunction with national surveys. Emissions of most of the major health-damaging pollutants (HDP) and many of the gases that contribute to GHG emissions from cooking stoves are the result of the significant portion of fuel carbon that is diverted to products of incomplete combustion (PIC) as a result of poor combustion efficiencies. The approximately linear increase in emissions of PIC with decreasing combustion efficiencies allows development of linear models to predict emissions of GHG and HDP intrinsically linked to CO2 and PIC production, and ultimately allows the prediction of global warming contributions from residential stove emissions. A comprehensive emissions database of three burn cycles of 23 typical fuel/stove combinations tested in a simulated village house in China has been used to develop models to predict emissions of HDP and global warming commitment (GWC) from cooking stoves in China, that rely on simple survey information on stove and fuel use that may be incorporated into national surveys. Stepwise regression models predicted 66% of the variance in global warming commitment (CO2, CO, CH4, NOx, TNMHC) per 1 MJ delivered energy due to emissions from these stoves if survey information on fuel type was available. Subsequently if stove type is known, stepwise regression models predicted 73% of the variance. Integrated assessment of policies to change stove or fuel type requires that implications for environmental impacts, energy efficiency, global warming and human exposures to HDP emissions can be evaluated. Frequently, this involves measurement of TSP or CO as the major HDPs. Incorporation of this information into models to predict GWC predicted 79% and 78% of the variance respectively. Clearly, however, the complexity of making multiple measurements in conjunction with a national survey would be both expensive and time consuming. Thus, models to predict HDP using simple survey information, and with measurement of either CO/CO2 or TSP/CO2 to predict emission factors for the other HDP have been derived. Stepwise regression models predicted 65% of the variance in emissions of total suspended particulate as grams of carbon (TSPC) per 1 MJ delivered if survey information on fuel and stove type was available and 74% if the CO/CO2 ratio was measured. Similarly stepwise regression models predicted 76% of the variance in COC emissions per MJ delivered with survey information on stove and fuel type and 85% if the TSPC/CO2 ratio was measured. Ultimately, with international agreements on emissions trading frameworks, similar models based on extensive databases of the fate of fuel carbon during combustion from representative household stoves would provide a mechanism for computing greenhouse credits in the residential sector as part of clean development mechanism frameworks and monitoring compliance to control regimes.     

Seasonal changes of CO(2), CH(4) and N(2)O fluxes in relation to land-use change in tropical peatlands located in coastal area of South Kalimantan

Tropical peatland could be a source of greenhouse gases emission because it contains large amounts of soil carbon and nitrogen. However these emissions are strongly influenced by soil moisture conditions. Tropical climate is characterized typically by wet and dry seasons. Seasonal changes in the emission of carbon dioxide (CO(2)), methane (CH(4)) and nitrous oxide (N(2)O) were investigated over a year at three sites (secondary forest, paddy field and upland field) in the tropical peatland in South Kalimantan, Indonesia. The amount of these gases emitted from the fields varied widely according to the seasonal pattern of precipitation, especially methane emission rates were positively correlated with precipitation. Converting from secondary forest peatland to paddy field tended to increase annual emissions of CO(2) and CH(4) to the atmosphere (from 1.2 to 1.5 kg CO(2)-C m(-2)y(-1) and from 1.2 to 1.9 g CH(4)-C m(-2)y(-1)), while changing land-use from secondary forest to upland tended to decrease these gases emissions (from 1.2 to 1.0 kg CO(2)-C m(-2)y(-1) and from 1.2 to 0.6 g CH(4)-C m(-2)y(-1)), but no clear trend was observed for N(2)O which kept negative value as annual rates at three sites.     

Remote sensing-based estimates of annual and seasonal emissions from crop residue burning in the contiguous United States

Crop residue burning is an extensive agricultural practice in the contiguous United States (CONUS). This analysis presents the results of a remote sensing-based study of crop residue burning emissions in the CONUS for the time period 2003-2007 for the atmospheric species of carbon dioxide (CO2), methane (CH4), carbon monoxide (CO), nitrogen dioxide (NO2, sulfur dioxide (SO2), PM2.5 (particulate matter [PM] < or = 2.5 microm in aerodynamic diameter), and PM10 (PM < or = 10 microm in aerodynamic diameter). Cropland burned area and associated crop types were derived from Moderate Resolution Imaging Spectroradiometer (MODIS) products. Emission factors, fuel load, and combustion completeness estimates were derived from the scientific literature, governmental reports, and expert knowledge. Emissions were calculated using the bottom-up approach in which emissions are the product of burned area, fuel load, and combustion completeness for each specific crop type. On average, annual crop residue burning in the CONUS emitted 6.1 Tg of CO2, 8.9 Gg of CH4, 232.4 Gg of CO, 10.6 Gg of NO2, 4.4 Gg of SO2, 20.9 Gg of PM2.5, and 28.5 Gg of PM10. These emissions remained fairly consistent, with an average interannual variability of crop residue burning emissions of +/- 10%. The states with the highest emissions were Arkansas, California, Florida, Idaho, Texas, and Washington. Most emissions were clustered in the southeastern United States, the Great Plains, and the Pacific Northwest. Air quality and carbon emissions were concentrated in the spring, summer, and fall, with an exception because of winter harvesting of sugarcane in Florida, Louisiana, and Texas. Sugarcane, wheat, and rice residues accounted for approximately 70% of all crop residue burning and associated emissions. Estimates of CO and CH4 from agricultural waste burning by the U.S. Environmental Protection Agency were 73 and 78% higher than the CO and CH4 emission estimates from this analysis, respectively. This analysis also showed that crop residue burning emissions are a minor source of CH4 emissions (< 1%) compared with the CH4 emissions from other agricultural sources, specifically enteric fermentation, manure management, and rice cultivation.     

Swine wastewater treatment using attached-growth and suspended-growth two stage sequencing batch reactors with real-time control.

Two two-stage sequencing batch reactors (TSSBR), one attached-growth and one suspended-growth, were operated under three levels of wastewater concentration (approximately 4,000, 2,000 and 500 TOC mg/L), respectively, to compare the pH and ORP (oxidation-reduction potential) patterns and system performance. In both TSSBR systems, the pH and ORP profiles varied with organic loading yet exhibited consistent patterns with distinctive features suitable for real-time control. For all runs at the three levels of influent, both systems achieved similar levels of treatment for BOD5, TOC and TSS of over 97.5, 93.4, and 97.3%, respectively. The attached-growth system out performed the suspended-growth system in achieving the same levels of treatment at much shorter aeration cycle times. The treatment efficiency for NO3(-)-N and PO4(-3) was greatly affected by the carbon content in the wastewater, and the best treatment was achieved during the TOC approximately 4,000 mg/L runs with final effluent at 4.0 and 21.3 mg/L, respectively.     

Greenhouse gas emissions estimation from proposed El Fukhary Landfill in the Gaza Strip

Landfills throughout the world are contributing to the global warming problem. This is due to the existence of the most important greenhouse gases (GHG) in landfill gas (LFG); namely, methane (CH4) and carbon dioxide (CO2). The aim of this paper is quantifying the total potential emissions, as well as the variation in production with time of CH4 from a proposed landfill (El Fukhary landfill) in the Gaza Strip, Palestine. Two different methods were adopted in order to quantify the total potential CH4 emissions; the Default methodology based on the intergovernmental panel on climate change (IPCC) 1996 revised guidelines and the Landfill Gas Emissions model (LandGEM V3.02) provided by the United States Environmental Protection Agency (EPA). The second objective of the study has been accomplished using the Triangle gas production model. The results obtained from both Default and LandGEM methods were found to be nearly the same. For 25 years of disposing MSW, El Fukhary landfill expected to have potential CH4 emissions of 1.9542 ± 0.0037 ×109 m3. Triangle model showed that the peak production in term of CH4 would occur in 2043; 28 years beyond the open year. Moreover, the model shows that 50 % of the gas will be produced approximately at the middle of the total duration of gas production. Proper control of Methane emissions from El Fukhary landfill is highly suggested in order to reduce the harmful effects on the environment.

Implications: Although, GHG emissions are extensively discussed in the developed countries throughout the world, it has gained little concern in the developing countries because they are forced most of the time to put environmental concerns at the end of their priority list. The paper shows that developing countries have to start recognizing their fault and change their way of dealing with environmental issues especially GHG emissions (mainly Methane and carbon dioxide). The authors estimated the potential methane emissions from a proposed central landfill that has been approved to be built in Palestine, a country that is classified as a developing country.     

Monitoring the multi-year carbon balance of a subarctic palsa mire with micrometeorological techniques

This article reports a dataset on 8 years of monitoring carbon fluxes in a subarctic palsa mire based on micrometeorological eddy covariance measurements. The mire is a complex with wet minerotrophic areas and elevated dry palsa as well as intermediate sub-ecosystems. The measurements document primarily the emission originating from the wet parts of the mire dominated by a rather homogenous cover of Eriophorum angustifolium. The CO(2)/CH(4) flux measurements performed during the years 2001-2008 showed that the areas represented in the measurements were a relatively stable sink of carbon with an average annual rate of uptake amounting to on average -46 g C m(-2) y(-1) including an equally stable loss through CH(4) emissions (18-22 g CH(4)-C m(-2) y(-1)). This consistent carbon sink combined with substantial CH(4) emissions is most likely what is to be expected as the permafrost under palsa mires degrades in response to climate warming.     

Methane emissions responding to Azolla inoculation combined with midseason aeration and N fertilization in a double-rice cropping system

Environmental Science and Pollution Research - Methane (CH4) is an important greenhouse gas (GHG), and paddy fields are major sources of CH4 emissions. This pot experiment was conducted to...     

Fluxes of methane,carbon dioxide and nitrous oxide in boreal lakes and potential anthropogenic effects on the aquatic greenhouse gas emissions

We have examined how some major catchment disturbances may affect the aquatic greenhouse gas fluxes in the boreal zone, using gas flux data from studies made in 1994-1999 in the pelagic regions of seven lakes and two reservoirs in Finland. The highest pelagic seasonal average methane (CH(4)) emissions were up to 12 mmol x m(-2) x d(-1) from eutrophied lakes with agricultural catchments. Nutrient loading increases autochthonous primary production in lakes, promoting oxygen consumption and anaerobic decomposition in the sediments and this can lead to increased CH(4) release from lakes to the atmosphere. The carbon dioxide (CO(2)) fluxes were higher from reservoirs and lakes whose catchment areas were rich in peatlands or managed forests, and from eutrophied lakes in comparison to oligotrophic and mesotrophic sites. However, all these sites were net sources of CO(2) to the atmosphere. The pelagic CH(4) emissions were generally lower than those from the littoral zone. The fluxes of nitrous oxide (N(2)O) were negligible in the pelagic regions, apparently due to low nitrate inputs and/or low nitrification activity. However, the littoral zone, acting as a buffer for leached nitrogen, did release N(2)O. Anthropogenic disturbances of boreal lakes, such as increasing eutrophication, can change the aquatic greenhouse gas balance, but also the gas exchange in the littoral zone should be included in any assessment of the overall effect. It seems that autochthonous and allochthonous carbon sources, which contribute to the CH(4) and CO(2) production in lakes, also have importance in the greenhouse gas emissions from reservoirs.     

Agriculture's share in the emission of trace gases affecting the climate and some cause-oriented proposals for sufficiently reducing this share

This paper discusses agriculture's share in the world-wide emissions of climate-affecting gases and in the global warming potential (GWP). Proposals also are presented to reduce these emissions adequately, using a cause-oriented approach. Largely due to the fertilization and cultivation of agriculture as well as the burning of biomass, agriculture has a very high share in the anthropogenic emissions of NH(3), N(2)O, CH(4) and CO at >95%, 81%, 70% and 52%, respectively, while its share in the NO(x) and CO(2) emissions is relatively small at 35% and 21%. The GWP of agriculture, based on annually 16.1 x 10(9) tons of CO(2), approaches 63% of the GWP of the energy sector or 80% of the GWP of its CO(2) emissions. At 34% and 32%, respectively, the main originators in the GWP of agriculture would seem to be CO(2) (changing land use) and CH(4) (animal husbandry/rice cropping/biomass burning) followed at 15% by NO(2) (technical and biological N fixation/(cultivation and recultivation/biomass burning) and 10% and 9% by CO and NO(x). The GWP of 3 German dairy cows corresponds with 13.2 tonnes CO(2) per year the GWP of two average German automobiles. However, the ozone-destroying effect of N(2)O and the climate-relevant effects of NH(3) are not yet included here. As with the therapy for other 'modern' boundary-crossing environmental damages, such as acidification or eutrophication, global climate change therapy likewise needs a therapy for the respective effects of reactive compounds of carbon, nitrogen, phosphorous, and sulfur also emitted by agriculture. Proposals for reducing these emissions within the agricultural sector include need-oriented plant, animal and human nutrition, more efficient external and internal nutrient recycling, the cessation of further clearing by burning, along with intensified afforestation mainly in the tropics, targeted measures to reduce nutrient losses/emissions, and measures for more efficient use of nutrients in plant, animal and human nutrition. These measures would at best result in reduced pollution of the global environment but not put it to an end. Decisive, therefore, is both the tolerable extent of mankind and its long-term sustainable way of life.     

Air emissions of ammonia and methane from livestock operations: valuation and policy options

The animal husbandry industry is a major emitter of ammonia (NH3), which is a precursor of fine particulate matter (PM2.5)--arguably, the number-one environment-related public health threat facing the nation. The industry is also a major emitter of methane (CH4), which is an important greenhouse gas (GHG). We present an integrated process model of the engineering economics of technologies to reduce NH3 and CH4 emissions at dairy operations in California. Three policy options are explored: PM offset credits for NH3 control, GHG offset credits for CH4 control, and expanded net metering policies to provide revenue for the sale of electricity generated from captured methane (CH4) gas. Individually these policies vary substantially in the economic incentives they provide for farm operators to reduce emissions. We report on initial steps to fully develop the integrated process model that will provide guidance for policy-makers.     

Non-controlled biogenic emissions to the atmosphere from Lazareto landfill, Tenerife, Canary Islands

GOAL, SCOPE AND BACKGROUND: [corrected] Historically, landfills have been the simplest form of eliminating urban solid waste with the minimum cost. They have been the most usual method for discarding solid waste. However, landfills are considered authentic biochemical reactors that introduce large amounts of contaminants into the environment in the form of gas and leachates. The dynamics of generation and the movement of gas in landfills depend on the input and output parameters, as well as on the structure of the landfill and the kind of waste. The input parameters include water introduced through natural or artificial processes, the characteristics of the urban solid waste, and the input of atmospheric air. The main output parameters for these biochemical reactors include the gases and the leachates that are potentially pollutants for the environment. Control systems are designed and installed to minimize the impact on the environment. However, these systems are not perfect and a significant amount of landfill gas could be released to the atmosphere through the surface in a diffuse form, also known as Non-controlled emission. In this paper, the results of the Non-controlled biogenic gas emissions from the Lazareto landfill in Tenerife, Canary Islands, are presented. The purpose of this study was to evaluate the concentration of CH4 and CO2 in the soil gas of the landfill cover, the CH4 and CO2 efflux from the surface of the landfill and, finally, to compare these parameters with other similar landfills. In this way, a better understanding of the process that controls biogenic gas emissions in landfills is expected. METHODS: A Non-controlled biogenic gas emission survey of 281 sampling sites was carried out during February and March, 2002. The sampling sites were selected in order to obtain a well-distributed sampling grid. Surface landfill CO2 efflux measurements were carried out at each sampling site on the surface landfill together with soil gas collection and ground temperatures at a depth of 30-40 cm.The CH4 efflux was computed from CO2 efflux and from the ratio CH4/CO2 in the soil gas. Soil gas samples were collected at a depth of 30-40 cm using a metallic probe and 20 cc hypodermic syringes, and later stored in evacuated 10 cc vacutainers for laboratory analysis of bulk composition. The gas sample was introduced in a vacutainer filled with deionized water and displacing the water until the vacutainer was filled with the gas sample in order to avoid air contamination from entering. The surface landfill temperature of the landfill was measured at a depth of 40 cm using a digital thermometer type OMEGA 871A. Landfill gases, CO2 and CH4, were analyzed within 24 hours using a double channel VARIAN micro-GC QUAD CP-2002P, with a 10 meter PORAPLOT-Q column, a TCD detector, and He as a carrier gas. The analysis temperature was 40 degrees C and the injection time was 10 msec. Surface landfill CO2 efflux measurements were performed using a portable NDIR spectrophotometer Licor-800 according to the accumulation chamber method (Chiodini et al. 1996). The data treatment, aimed at drawing the flux map and computing the total gas output, was based on the application of stochastic simulation algorithms provided by the GSLIB program (Deutsch and Journel 1998). RESULTS: Diffuse CH4 and CO2 efflux values range from negligible values up to 7,148 and 30,573 g m(-2) d(-1), respectively. The spatial distribution of the concentration and efflux of CO2, CH4 and soil temperature, show three areas of maximum activity in the landfill, suggesting a non-uniform pattern of diffuse degassing. This correlation between high emissions and concentration of CO2, CH4 and soil temperatures suggests that the areas of higher microbial activity and exothermic reactions are releasing CO2 and CH4 to the atmosphere from the landfill. Taking into consideration the spatial distribution of the CO2 and CH4 efflux values as well as the extension of the landfill, the Non-controlled emission of CO2 and CH4 to the atmosphere by the Lazareto's landfill are of 167 +/- 13.3 and 16 +/- 2.5 t d(-1), respectively. DISCUSSION: The patterns of gas flow within the landfill seem to be affected by boundary materials at the sides. The basalt layers have a low permeability and the gas flow in these areas is extensive. In this area, where a basalt layer does not exist, the flow gas diffuses toward the sea and the flux emissions at the landfill surface are lower. This behavior reflects the possible dissolution of gases into water and the deflection of gases towards the surface at the basalt boundary. The proximity to the sea, the installation of a palm tree garden and, as a result, the contribution of water coming from the watering of this garden has reactivated the system. The introduction of sea water into the landfill and the type of boundary could be defining the superficial gas discharges. CONCLUSIONS: Results from this study indicate that the spatial distribution of Non-controlled emission of CO2 and CH4 at the Lazareto's landfill shows a non-uniform pattern of diffuse degassing. The northeast, central and northwest areas of the Lazareto's landfill are the three areas of high emissions and concentration of CO2 and CH4, and high temperatures. The correlation between high emissions and the concentration of CO2, CH4, and the high temperatures suggest that the areas of higher microbial activity and exothermic reactions are releasing more CO2 and CH4 to the atmosphere from the landfill. A high concentration of CO2 is probably due to the presence of methanotrophic bacteria in the soil atmosphere of the landfill. Patterns of gas flow within the landfill seem to be affected by boundary materials (basalt layers) of low permeability, and side boundaries of the flux emissions at the surface are higher. At the sides of seawater and sediment boundaries, flux emissions at the landfill surface are lower. This behavior reflects a possible dissolution of gases into the water and the deflection of gases towards the surface at the basalt boundary. With this study, we can compare the data obtained in this landfill with other landfills and observe the different levels of emission. The proximity to the sea and the installation of the palm tree garden palms and, as a result, the contribution of water coming from the watering of this garden has reactivated the system. Many landfills worldwide located in similar settings could experience similar gas production processes. RECOMMENDATIONS AND PERSPECTIVES: The need for investigating and monitoring sea water and sediment quality in these landfills is advisable. Concentrations and fluxes of contaminants and their impact in the area should be assessed. With this study we can compare the data obtained in these landfills with other landfills and observe the different levels of emission.     

The carbon-sequestration potential of municipal wastewater treatment

The lack of proper wastewater treatment results in production of CO(2) and CH(4) without the opportunity for carbon sequestration and energy recovery, with deleterious effects for global warming. Without extending wastewater treatment to all urban areas worldwide, CO(2) and CH(4) emissions associated with wastewater discharges could reach the equivalent of 1.91 x 10(5) t(CO2)d(-1) in 2025, with even more dramatic impact in the short-term. The carbon sequestration benefits of wastewater treatment have enormous potential, which adds an energy conservation incentive to upgrading existing facilities to complete wastewater treatment. The potential greenhouse gases discharges which can be converted to a net equivalent CO(2) credit can be as large as 1.91 x 10(5) t(CO2)d(-1) in 2025 by 2025. Biomass sequestration and biogas conversion energy recovery are the two main strategies for carbon sequestration and emission offset, respectively. The greatest potential for improvement is outside Europe and North America, which have largely completed treatment plant construction. Europe and North America can partially offset their CO(2) emissions and receive benefits through the carbon emission trading system, as established by the Kyoto protocol, by extending existing technologies or subsidizing wastewater treatment plant construction in urban areas lacking treatment. This strategy can help mitigate global warming, in addition to providing a sustainable solution for extending the health, environmental, and humanitarian benefits of proper sanitation.     

A new model of tropospheric hydroxyl radical concentrations

A chemistry model of the global troposphere is presented which focuses on the hydroxyl radical, OH. Global distributions of OH are calculated based on known chemical reaction pathways, experimentally measured values of precursor species O3, H2O, NOx (defined as NO+NO2), CO, CH4, and actinic flux (which includes the effects of cloud cover and O3 column absorption). Model grid resolution is 1 km in altitude by 10 degrees latitude, and zonally divided into land or ocean. Species are calculated as seasonal averages. Global annual mean OH in the troposphere (up to 14 km altitude) is calculated to be 9.2 x 10(5) molcm(-3) with averages of 9.8 x 10(5) in the northern hemisphere, and 8.5 x 10(5) in the southern hemisphere. Global CO and CH(4) oxidation rates by OH are calculated to be 1840 Tgyear(-1) and 580 Tgyear(-1), respectively. OH is found to be most sensitive to O3 and H2O concentrations, as well as to the photolysis rate of O3 to O1D. Sensitivity of CO and CH4 oxidation rates to cloud presence shows an inverse relationship to cloud amount and optical depth. Model results are shown to be consistent with results from two other published models.     

A greenhouse gas emissions inventory for Pennsylvania

The Pennsylvania greenhouse gas (GHG) emissions inventory presented in this paper provides detailed estimates of emissions and their sources for the six major categories of GHGs. The inventory was compiled using the current U.S. Environment Protection Agency methodology, which applies emissions factors to socioeconomic data, such as fossil energy use, vehicle miles traveled, and industrial production. The paper also contains an assessment of the methodology and suggestions for improving accounting with respect to process, sectoral, and geographic considerations. The study found that Pennsylvania emitted 77.4 million metric tons carbon equivalent of GHGs in 1990 and that this total increased by 3% to 79.8 million metric tons carbon equivalent by 1999. Despite this increase, however, the state's percentage contribution to the United States total declined during the decade. Pennsylvania's carbon dioxide (CO2) emissions from fossil fuels represented 92.4% of 1990 totals and declined to 90.5% in 1999. Electricity generation was the largest single source of CO2 emissions, being responsible for 38% of fossil fuel CO2 emissions in 1990 and 40% of the total in 1999. Transportation emissions accounted for the largest increases in emissions between 1990 and 1999, whereas industrial emissions accounted for the largest decrease. The overall trend indicates that Pennsylvania has been able to weaken the relationship between GHG emissions and economic growth.     

Note on In-Traffic Measurement of Airborne Tire-Wear Participate Debris

Measuring greenhouse gas (GHG) source emissions provides data for validation of GHG inventories, which provide the foundation for climate change mitigation. Two Toyota RAV4 electric vehicles were outfitted with high-precision instrumentation to determine spatial and temporal resolution of GHGs (e.g., nitrous oxide, methane [CH₄], and carbon dioxide [CO₂]), and other gaseous species and particulate metrics found near emission sources. Mobile measurement platform (MMP) analytical performance was determined over relevant measurement time scales. Pollutant residence times through the sampling configuration were measured, ranging from 3 to 11 sec, enabling proper time alignment for spatial measurement of each respective analyte. Linear response range for GHG analytes was assessed across expected mixing ratio ranges, showing minimal regression and standard error differences between 5, 10, 30, and 60 sec sampling intervals and negligible differences between the two MMPs. GHG instrument drift shows deviation of less than 0.8% over a 24-hr measurement period. These MMPs were utilized in tracer-dilution experiments at a California landfill and natural gas compressor station (NGCS) to quantify CH₄ emissions. Replicate landfill measurements during October 2009 yielded annual CH₄ emissions estimates of 0.10 ± 0.01, 0.11 ± 0.01, and 0.12 ± 0.02 million tonnes of CO₂ equivalent (MTCO₂E). These values compare favorably to California GHG Emissions Inventory figures for 2007, 2008, and 2009 of 0.123, 0.125, and 0.126 MTCO₂E/yr, respectively, for this facility. Measurements to quantify NGCS boosting facility-wide emissions, during June 2010 yielded an equivalent of 5400 ± 100 TCO₂E/yr under steady-state operation. However, measurements during condensate transfer without operational vapor recovery yield an instantaneous emission rate of 2–4 times greater, but was estimated to only add 12 TCO₂E/yr overall. This work displays the utility for mobile GHG measurements to validate existing measurement and modeling approaches, so emission inventory values can be confirmed and associated uncertainties reduced.

Implications:?Measuring greenhouse gas (GHG) source emissions provides data and validation for GHG inventories, the foundation for climate change mitigation. Mobile measurement platforms with robust analytical instrumentation completed tracer-dilution experiments in California at a landfill and natural gas compressor station (NGCS) to quantify CH₄ emissions. Data collected for landfill CH₄ agree with the current California emissions inventory, while NGCS data show the possible variability from this type of facility. This work displays the utility of mobile GHG measurements to validate existing measurement and modeling approaches, such that emission inventory values can be confirmed, associated uncertainties reduced, and mitigation efforts quantified.     

Fluxes of N2O, CH4 and CO2 in a meadow ecosystem exposed to elevated ozone and carbon dioxide for three years

Open-top chambers (OTCs) were used to evaluate the effects of moderately elevated O3 (40-50 ppb) and CO2 (+100 ppm) and their combination on N2O, CH4 and CO2 fluxes from ground-planted meadow mesocosms. Bimonthly measurements in 2002-2004 showed that the daily fluxes of N2O, CH4 and CO2 reacted mainly to elevated O3, while the fluxes of CO2 also responded to elevated CO2. However, the fluxes did not show any marked response when elevated O3 and CO2 were combined. N2O and CO2 emissions were best explained by soil water content and air and soil temperatures, and they were not clearly associated with potential nitrification and denitrification. Our results suggest that the increasing O3 and/or CO2 concentrations may affect the N2O, CH4 and CO2 fluxes from the soil, but longer study periods are needed to verify the actual consequences of climate change for greenhouse gas emissions.     

Ferrate(VI): green chemistry oxidant for degradation of cationic surfactant

Iron in its familiar form exists in the +2 and +3 oxidation states, however, higher oxidation state of iron +6, ferrate(VI) (Fe(VI)O(4)(2-)) can be obtained. The high oxidation power of ferrate(VI) can be utilized in developing cleaner ("greener") technology for remediation processes. This paper demonstrates the unique property of ferrate(VI) to degrade almost completely the cationic surfactant, cetylpyridinium chloride (C(5)H(5)N(+)(CH(2))(15)CH(3).H(2)O Cl(-), CPC). The Rate law for the oxidation of CPC by ferrate(VI) at pH 9.2 was found to be: -d[Fe(VI)]/dt = k[Fe(VI)][CPC](2). Ferrate(VI) oxidizes CPC within minutes and molar consumption of ferrate(VI) was nearly equal to the oxidized CPC. The decrease in total organic carbon (TOC) from CPC was more than 95%; suggesting mineralization of CPC to carbon dioxide. Ammonium ion was the other product of the oxidation. This is the first report in which Fe(VI)O(4)(2-) ion opens the pyridine ring and mineralizes the aliphatic chain of the organic molecule giving inorganic ions.