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Environmental Trade-Offs for a Process Utilizing Aerobic Respiration for Biological Conversion of Cellulosic Biomass-Derived Sugars to Hydrocarbons (Renewable Diesel Blendstock): Cooperative Research and Development Final Report, CRADA Number CRD-18-00765, Project 1

Phase II work is meant to develop an advanced understanding of how production of a renewable diesel blendstock from lignocellulosic biomass feedstocks via aerobic respiration at different production scales affects emissions of criteria pollutants and greenhouse gases (GHGs), local and regional air quality. The results could inform decisions by stakeholders (e.g., industry, community, air quality planners, investors) regarding relationships and tradeoffs between multiple environmental impacts and the challenges and opportunities for the design and deployment of a sustainable biofuel supply chain.

09 BIOMASS FUELS↗

Zymomonas mobilis oxidative stress transcriptomics

Zymomonas mobilis is an important bioenergy organism that has potential to produce biofuels, including ethanol, in high volumes. Here we examined the response of Zymomonas mobilis to various oxidative stresses using genome-scale transcriptomics data. We first examined the transcrpit abundance in WT aerobic growth compared to aerobic grown in paraquat, which forms superoxide. Under anaerobic growth conditions we compared WT Zymomonas mobilis with strains grown in media lacking iron as well as strains lacking iron that were treated with the iron chelator DIP before collection. Finally we examined transcript abundance in cells lacking ZMO_0422 (Rrf2 family transcription factor homolog) and ZMO_1411 (Fur homolog) grown under anaerobic conditions. Overall design: Transcriptomic analysis of WT, a deletion of ZMO_0422, and a deletion of ZMO_1411 in Zymomonas mobilis ZM4 under aerobic and anaerobic growth conditions along with various oxidative stresses: Paraquate addition, No Iron, and hydrogen peroxide addition.

aerobic↗

The Study of Biomass Emissions for Defining Radiative Forcing of Climate

Accurate quantification of the amounts of trace gases and particulate matter emitted from vegetation fires and other sources of biomass burning (agricultural waste and biofuels) on a regional and global basis is required by a number of users, including scientists studying a wide range of atmospheric processes, national governments who are required to report greenhouse gas emissions, and those interested in quantifying the sources of air pollution that affect human health at regional scales. Over the past decade, improvements in the ability to detect and map fires using a number of different satellite systems have been achieved, largely through efforts coordinated through working groups organized by the IGBP Data and Information System and Global Observation of Forest Cover (GOFC) projects. In addition, significant advances and improvement in or understanding of the emissions factors for biomass burning in different biomes has resulted through efforts by the Biomass Burning Experiment (BIBEX) organized through the International Global Atmospheric Chemistry project. A number of satellite-based fire data products have been generated, and a number of new products will shortly be available. These new data products will provide the basis for estimating emissions from biomass burning on a global basis. However, a number of issues remain concerning the availability of other data sets needed to generate these estimates. Recognizing these issues, the GOFC-Fire Satellite Validation Workshop (held in Lisbon, Portugal on 9-11 July 2001), recommended that a workshop focusing on Improving Global Estimates of Atmospheric Emissions from Biomass Burning be organized. This workshop was held from 17- 19 July 2002 on the campus of the University of Maryland, College Park, Maryland. This workshop served as the annual meeting of the GOFC/GOLD-Fire Program. The overall goals of the meeting were to review the information products generated from satellite imagery and other sources that are currently available for developing emission estimates from biomass burning, evaluate areas where improved or additional products would be beneficial, and recommend products for use by the atmospheric science community.

Penner, Joyce↗

Elevated Ozone in the Troposphere over the Atlantic and Pacific Oceans in the Northern Hemisphere

Tropospheric column ozone (TCO) is derived from differential measurements of total column ozone from Nimus-7 and Earth Probe TOMS, and stratospheric column ozone from the Microwave Limb Sounder instrument on the Upper Atmospheric Research Satellite. It is shown that TCO during summer months over the Atlantic and Pacific Oceans at northern mid-latitudes is about the same (50-60 Dobson Units) as over the continents of North America, Europe and Asia, where surface emissions of nitrogen oxides from industrial sources, biomass and biofuel burning and biogenic emissions are significantly larger. This nearly uniform zonal variation in TCO is modulated by surface topography of the Rocky and Himalayan mountains and Tibetan Plateau where TCO is reduced by 20-30 Dobson Units. The zonal characteristics of TCO derived from satellite measurements are well simulated by a global chemical transport model called MOZART-2 (Model of Ozone and Related Chemical Tracers, version 2). The model results are analyzed to delineate the relative importance of various processes contributing to observed zonal characteristics of TCO, and they are shown that the surface emission of NOx contributes about 50% of the TCO at northern mid-latitudes, especially over the continents of North America, Europe and Asia. The result of TCO derived from TOMS and the analysis from MOZART-2 indicate that TCO is a very useful tool to study tropospheric O3 pollution resulting from surface emissions of pollutants.

Chandra, S.↗

Elevated Tropospheric Ozone over the Atlantic

Tropospheric column ozone (TCO) is derived from differential measurements of TOMS total column ozone and Microwave Limb Sounder stratospheric column ozone. It is shown that TCO during summer months over the Atlantic and Pacific Oceans in northern midlatitudes is about the same (50 to 60 Dobson Units) as over the continents of North America, Europe, and Asia, where surface emissions of nitrogen oxides from industrial sources, biomass and biofuel burning and biogenic emissions are significantly larger. This nearly uniform zonal variation in TCO is modulated by surface topography of the Rocky and Himalayan mountains, and Tibetan plateau where TCO is reduced by 20 to 30 Dobson Units. The zonal variation in TCO is well simulated by a global chemical transport model called MOZART-2 (Model of Ozone and Related Chemical Tracers, version 2). The model results are analyzed to delineate the relative importance of various processes contributing to observed zonal characteristics of TCO.

Chandra, S.↗

Processes Affecting Tropospheric Ozone over Africa

This is a Workshop Report prepared for Eos, the weekly AGU magazine, The workshop took place between 26-28 January 2004 at the University of KwaZulu-Natal in Durban, South Africa and was attended by 26 participants (http//www.geography.und.ac.za). Considerable progress has been made in ozone observations except for northern Africa (large data gaps) and west Africa (to be covered by the French-sponsored AMMA program). The present-day ozone findings were evaluated and reviewed by speakers using Aircraft data (MOZAIC program), NASA satellites (MOPITT, TRMM, TOMS) and ozone soundings (SHADOZ). Besides some ozone gaps, there are challenges posed by the need to assess the relative strengths of photochemical and dynamic influences on the tropospheric ozone budget. Biogenic, biofuels, biomass burning sources of ozone precursors remain highly uncertain. Recent findings (by NASA's Chatfield and Thompson, using satellite and sounding data) show significant impact of Indian Ocean pollution on African ozone. European research on pollutants over the Mediterranean and the middle east, that suggests that ozone may be exported to Africa from these areas, also needs to be considered.

Diab, Roseanne D.↗

Tropospheric Ozone Climatology over Irene, South Africa, From 1990-1994 and 1998-2002

This paper describes ozone profiles from sonde data during the period of NASA s TRACE-A and the more recent SHADOZ (Southern Hemisphere Additional Ozonesondes) period. The data were taken by the South African Weather Service at the Irene (25 deg.54 min S; 28 deg. 13 min. E) station near Pretoria, South Africa, an area that is a unique mixture of local industry, heavy biofuels use and importation of biomass burning ozone from neighboring countries to the north. The main findings are: (1) With its geographical position at the edge of the subtropical transition zone, mid- latitude dynamical influences are evident at Irene, predominantly in winter when upper tropospheric ozone is enhanced as a result of stratospheric-tropospheric exchange. (2) There has been an increase in the near-surface ozone amount between the early 1990s and a decade later, presumably due to an influx of rural population toward the Johannesburg-Pretoria area, as well as with industrial growth and development. (3) Most significant for developing approaches for satellite ozone profile climatologies, cluster analysis has enabled the delineation of a background and "most polluted" profile. Enhancements of at least 30% occur throughout the troposphere in spring and in certain layers increases of 100 % are observed.

Diab, R. D.↗

Biologically Derived Nanoparticle Arrays via a Site-Specific Reconstitution of Ferritin and their Electrochemistry

Nanoparticle arrays biologically derived from an electrochemically-controlled site-specific biomineralization were fabricated on a gold substrate through the immobilization process of biomolecules. The work reported herein includes the immobilization of ferritin with various surface modifications, the electrochemical biomineralization of ferritins with different inorganic cores, the fabrication of self-assembled arrays with the immobilized ferritin, and the electrochemical characterization of various core materials. Protein immobilization on the substrate is achieved by anchoring ferritins with dithiobis-N-succinimidyl propionate (DTSP). A reconstitution process of electrochemical site-specific biomineralization with a protein cage loads ferritins with different core materials such as Pt, Co, Mn, and Ni. The ferritin acts as a nano-scale template, a biocompatible cage, and a separator between the nanoparticles. The nano-sized metalcored ferritins on a gold substrate displayed a good electrochemical activity for the electron transport and storage, which is suitable for bioelectronics applications such as biofuel cell, bionanobattery, biosensors, etc. Keywords: Ferritin, immobilization, site-specific reconstitution, biomineralization, and bioelectronics

Kim, Jae-Woo↗

Chemical Composition of Asian Continental Outflow over the Western Pacific: Results from Transport and Chemical Evolution over the Pacific (TRACE-P)

We characterize the chemical composition of Asian continental outflow observed during the NASA Transport and Chemical Evolution over the Pacific (TRACE-P) mission during February-April 2001 in the western Pacific using data collected on the NASA DC-8 aircraft. A significant anthropogenic impact was present in the free troposphere and as far east as 150degE longitude reflecting rapid uplift and transport of continental emissions. Five-day backward trajectories were utilized to identify five principal Asian source regions of outflow: central, coastal, north-northwest(NNW), southeast (SE), and west-southwest (WSW). The maximum mixing ratios for several species, such as CO, C2Cl4, CH3Cl, and hydrocarbons, were more than a factor of 2 larger in the boundary layer of the central and coastal regions due to industrial activity in East Asia. CO was well correlated with C2H2, C2H6, C2Cl4, and CH3Cl at low altitudes in these two regions (r(sup 2) approx. 0.77-0.97). The NNW, WSW, and SE regions were impacted by anthropogenic sources above the boundary layer presumably due to the longer transport distances of air masses to the western Pacific. Frontal and convective lifting of continental emissions was most likely responsible for the high altitude outflow in these three regions. Photochemical processing was influential in each source region resulting in enhanced mixing ratios of O3, PAN, HNO3, H2O2, and CH3OOH. The air masses encountered in all five regions were composed of a complex mixture of photcrchemically aged air with more recent emissions mixed into the outflow as indicated by enhanced hydrocarbon ratios (C2H2/CO greater than or equal to 3 and C3H8/C2H6 greater than or equal to 0.2). Combustion, industrial activities, and the burning of biofuels and biomass all contributed to the chemical composition of air masses from each source region as demonstrated by the H6, SO2, and C2Cl4 were compared for the TRACE-P and PEM-West B missions. In the more northern regions, O3, CO, and SO2 were higher at low altitudes during TRACE-P. In general, mixing ratios were fairly similar between the two missions in the southern regions. A comparison between CO/CO2, CO/CH4, C2H6/C3H8, NO(x)/SO2, and NO(y)/(SO2 + nss-SO4) ratios for the five source regions and for the 2000 Asian emissions summary showed vay close agreement indicating that Asian emissions were well represented by the TRACE-P data and tbe emissions inventory.

Russo, R. S.↗

Emissions from Miombo Woodland and Dambo Grassland Savanna Fires

Airborne measurements of trace gases and particles over and downwind of two prescribed savanna fires in Zambia are described. The measurements include profiles through the smoke plumes of condensation nucleus concentrations and normalized excess mixing ratios of particles and gases, emission factors for 42 trace gases and seven particulate species, and vertical profiles of ambient conditions. The fires were ignited in plots of miombo woodland savanna, the most prevalent savanna type in southern Africa, and dambo grassland savanna, an important enclave of miombo woodland ecosystems. Emission factors for the two fires are combined with measurements of fuel loading, combustion factors, and burned area (derived from satellite burn scar retrievals) to estimate the emissions of trace gases and particles from woodland and grassland savanna fires in Zambia and southern Africa during the dry season (May-October) of 2000. It is estimated that the emissions of CO2, CO, total hydrocarbons, nitrogen oxides (NOx as NO), sulfur dioxide (SO2), formaldehyde, methyl bromide, total particulate matter, and black carbon from woodland and grassland savanna fires during the dry season of 2000 in southern Africa contributed 12.3%, 12.6%, 5.9%, 10.3%, 7.5%, 24.2%, 2.8%, 17.5%, and 11.1%, respectively, of the average annual emissions from all types of savanna fires worldwide. In 2000 the average annual emissions of methane, ethane, ethene, acetylene, propene, formaldehyde, methanol, and acetic acid from the use of biofuels in Zambia were comparable to or exceeded dry season emissions of these species from woodland and grassland savanna fires in Zambia.

Sinha, Parikhit↗

Alternative Fuels and Their Potential Impact on Aviation

With a growing gap between the growth rate of petroleum production and demand, and with mounting environmental needs, the aircraft industry is investigating issues related to fuel availability, candidates for alternative fuels, and improved aircraft fuel efficiency. Bio-derived fuels, methanol, ethanol, liquid natural gas, liquid hydrogen, and synthetic fuels are considered in this study for their potential to replace or supplement conventional jet fuels. Most of these fuels present the airplane designers with safety, logistical, and performance challenges. Synthetic fuel made from coal, natural gas, or other hydrocarbon feedstock shows significant promise as a fuel that could be easily integrated into present and future aircraft with little or no modification to current aircraft designs. Alternatives, such as biofuel, and in the longer term hydrogen, have good potential but presently appear to be better suited for use in ground transportation. With the increased use of these fuels, a greater portion of a barrel of crude oil can be used for producing jet fuel because aircraft are not as fuel-flexible as ground vehicles.

Daggett, D.↗

Global Energy and Aviation Concerns

Renewable energy sources are usually diffuse and require large facilities. Biofuels work better, are more economical to produce for ground transportation, but sharply increase competition for food croplands. Noble laureate Richard Smalley (deceased-2005) conceptual 20 TWe power generation covers hundreds x hundreds of miles. Combined with Fuller s superconducting power grid system would enable renewable planetary energy. A solar-wind project in Australia will have a 7km diameter collector interfacing with a 1 km tower to extract 200 MW from wind turbines mounted at the base. GE Energy s 3.5MW Wind Turbine is large and placing this in perspective, it is as if one were rotating a Boeing 747-200; the blade diameter is that large. Wind turbines are rapidly gaining popularity in Europe and photovoltaic (PV) is expected to also expand rapidly. It becomes clear that we need (and still have time) to develop new sources of energy. Hf 178 bombarded by X-rays produces Gamma-rays for heating. The reaction stops when the X-rays stop; the half life is about 30 years and seems manageable vs 30 000 years. Water splitting needs to be perused as do ultra fast ultra intense laser applications in terms of fusion and new materials developments including new ways to strip and re-bind hydrogen into fuels. New methods and tools for development are being found in quantum mechanical applications to macro-systems and need to be developed into a set of new tool boxes for development of these new energy sources.

Hendricks, Robert C.↗

Electrochemically Controlled Reconstitution of Immobilized Ferritins for Bioelectronic Applications

Site-specific reconstituted nanoparticles were fabricated via electrochemically-controlled biomineralization through the immobilization of biomolecules. The work reported herein includes the immobilization of ferritin with various surface modifications, the electrochemical biomineralization of ferritins with different inorganic cores, and the electrocatalytic reduction of oxygen on the reconstituted Pt-cored ferritins. Protein immobilization on the substrate is achieved by anchoring ferritins with dithiobis-N-succinimidyl propionate (DTSP). A reconstitution process of site-specific electrochemical biomineralization with a protein cage loads ferritins with different core materials. The ferritin acts as a nano-scale template, a biocompatible cage, and a separator between the nanoparticles. This first demonstration of electrochemically controlled site-specific reconstitution of biomolecules provides a new tool for biomineralization and opens the way to produce the bio-templated nanoparticles by electrochemical control. The nanosized platinum-cored ferritins on gold displayed good catalytic activity for the electrochemical reduction of oxygen, which is applicable to biofuel cell applications. This results in a smaller catalyst loading on the electrodes for fuel cells or other bioelectronic devices.

Kim, Jae-Woo↗

Alternate Fuels for Use in Commercial Aircraft

The engine and aircraft Research and Development (R&D) communities have been investigating alternative fueling in near-term, midterm, and far-term aircraft. A drop in jet fuel replacement, consisting of a kerosene (Jet-A) and synthetic fuel blend, will be possible for use in existing and near-term aircraft. Future midterm aircraft may use a biojet and synthetic fuel blend in ultra-efficient airplane designs. Future far-term engines and aircraft in 50-plus years may be specifically designed to use a low- or zero-carbon fuel. Synthetic jet fuels from coal, natural gas, or other hydrocarbon feedstocks are very similar in performance to conventional jet fuel, yet the additional CO2 produced during the manufacturing needs to be permanently sequestered. Biojet fuels need to be developed specifically for jet aircraft without displacing food production. Envisioned as midterm aircraft fuel, if the performance and cost liabilities can be overcome, biofuel blends with synthetic jet or Jet-A fuels have near-term potential in terms of global climatic concerns. Long-term solutions address dramatic emissions reductions through use of alternate aircraft fuels such as liquid hydrogen or liquid methane. Either of these new aircraft fuels will require an enormous change in infrastructure and thus engine and airplane design. Life-cycle environmental questions need to be addressed.

Daggett, David L.↗

Alternate-Fueled Flight: Halophytes, Algae, Bio-, and Synthetic Fuels

Synthetic and biomass fueling are now considered to be near-term aviation alternate fueling. The major impediment is a secure sustainable supply of these fuels at reasonable cost. However, biomass fueling raises major concerns related to uses of common food crops and grasses (some also called "weeds") for processing into aviation fuels. These issues are addressed, and then halophytes and algae are shown to be better suited as sources of aerospace fuels and transportation fueling in general. Some of the history related to alternate fuels use is provided as a guideline for current and planned alternate fuels testing (ground and flight) with emphasis on biofuel blends. It is also noted that lessons learned from terrestrial fueling are applicable to space missions. These materials represent an update and additions to the Workshop on Alternate Fueling Sustainable Supply and Halophyte Summit at Twinsburg, OH, Oct. 17 to 18, 2007 (ref. 1).

Hendricks, R. C.↗

Lunar Regolith Biomining: Workshop Report

On May 5th and 6th, 2007, NASA Ames Research Center hosted a workshop entitled 'Lunar Regolith Biomining'. The workshop addressed the feasibility of biologically-based mining of the lunar regolith along with identification of views and concepts for moving this topic forward to NASA. Workshop presentations provided background in topics of interest that served as the foundation for discussion in the subsequent breakout sessions. The first topical area included the history, status, and issues with biomining on Earth to familiarize all attendees with current activities. These presentations related the primary considerations in existing biomining, e.g., microbes of choice, pH of reactions, time and temperature, specific mining applications and locations, and benefits and/or limitations of biomining. The second area reviewed existing research efforts addressing biomining of planetary surfaces (Mars, Moon), including microbial considerations, and chemical necessities in biomining and biofuel production. The last element pertained to other non-biological considerations and influences in biomining efforts on the lunar surface such as radiation fluxes and effects, and the application of small satellite experiments to learn more about the lunar and Martian surfaces. Following the presentations, the workshop attendees divided into three breakout sessions to discuss areas of interest in greater detail and to define next steps in determining the feasibility of lunar regolith biomining. Topics for each of the three breakout sessions included: 1) bio-communities of choice, target product(s), and suggested ground studies; 2) physical/environmental issues and ground studies; and 3) the development of reference experiments for the Astrobiology Small payloads Workshop. The results of the breakout sessions are summarized and a list of participants is included.

Dalton, Bonnie P.↗

Variability of Springtime Transpacific Pollution Transport During 2000-2006: The INTEX-5 Mission in the Context of Previous Years

We analyze the transport of pollution across the Pacific during the NASA INTEX-B (Intercontinental Chemical Transport Experiment Part 8) campaign in spring 2006 and examine how this year compares to the time period for 2000 through 2006. In addition to aircraft measurements of carbon monoxide (CO) collected during INTEX-B, we include in this study multi-year satellite retrievals of CO from the Measurements of Pollution in the Troposphere (MOPITT) instrument and simulations from the chemistry transport model MOZART-4. Model tracers are used to examine the contributions of different source regions and source types to pollution levels over the Pacific. Additional modeling studies are performed to separate the impacts of inter-annual variability in meteorology and .dynamics from changes in source strength. interannual variability in the tropospheric CO burden over the Pacific and the US as estimated from the MOPITT data range up to 7% and a somewhat smaller estimate (5%) is derived from the model. When keeping the emissions in the model constant between years, the year-to-year changes are reduced (2%), but show that in addition to changes in emissions, variable meteorological conditions also impact transpacific pollution transport. We estimate that about 113 of the variability in the tropospheric CO loading over the contiguous US is explained by changes in emissions and about 213 by changes in meteorology and transport. Biomass burning sources are found to be a larger driver for inter-annual variability in the CO loading compared to fossil and biofuel sources or photochemical CO production even though their absolute contributions are smaller. Source contribution analysis shows that the aircraft sampling during INTEX-B was fairly representative of the larger scale region, but with a slight bias towards higher influence from Asian contributions.

Pfister, G. G.↗

Secondary Forests from Agricultural Abandonment in Amazonia 2000-2009

Ongoing negotiations to include reducing emissions from tropical deforestation and forest degradation (REDD+) in a post-Kyoto climate agreement highlight the critical role of satellite data for accurate and transparent accounting of forest cover changes. In addition to deforestation and degradation, knowledge of secondary forest dynamics is essential for full carbon accounting under REDD+. Land abandonment to secondary forests also frames one of the key tradeoffs for agricultural production in tropical forest countries-whether to incentivize secondary forest growth (for carbon sequestration and biodiversity conservation) or low-carbon expansion of agriculture or biofuels production in areas of secondary forests. We examined patterns of land abandonment to secondary forest across the arc of deforestation in Brazil and Bolivia using time series of annual Landsat and MODIS data from 2000-2009. Rates of land abandonment to secondary forest during 2002-2006 were less than 5% of deforestation rates in these years. Small areas of new secondary forest were scattered across the entire arc of deforestation, rather than concentrated in any specific region of the basin. Taken together, our analysis of the satellite data record emphasizes the difficulties of addressing the pool of new secondary forests in the context of REDD+ in Amazonia. Due to the small total area of secondary forests, land sparing through agricultural intensification will be an important element of efforts to reduce deforestation rates under REDD+ while improving agricultural productivity in Amazonia.

Morton, Douglas↗