Evaluation of two adsorbents for diffusive sampling and thermal desorption-gas chromatographic analysis of monoterpenes in air

Tube type samplers with two different adsorbents, Chromosorb 106 and Tenax TA, were evaluated by laboratory experiments and field tests for simultaneous diffusive sampling of alpha-pinene, beta-pinene and delta 3-carene and subsequent thermal desorption-gas chromatographic analysis. No statistically significant effects of exposure time, concentrations of monoterpenes or relative humidity were found for samplers with Chromosorb 106 when running a factorial design, with the exception of the adsorption of delta 3-carene, for which some weak effects were noted. Samplers with Tenax TA were affected by the sampling time as well as the concentration for all terpenes, with a strong interaction effect between these two factors. The terpenes showed good storage stability on both adsorbents. No effect of back-diffusion was noted when using Chromosorb 106, while Tenax TA showed some back-diffusion effects. The uptake rates, in ml min-1, for the terpenes on Chromosorb 106 were 0.36 for alpha-pinene, 0.36 for beta-pinene and 0.40 for delta 3-carene. The corresponding average values on Tenax TA were 0.30 for alpha-pinene, 0.32 for beta-pinene and 0.38 for delta 3-carene. The field validation proved that diffusive sampling on Chromosorb 106 agreed well with pumped sampling on charcoal for stationary samples, while the personal samples indicated a discrepancy of 25% between Chromosorb 106 and charcoal samples. Tenax TA generally gave lower results than Chromosorb 106 in all field samples. Samplers packed with Chromosorb 106 could be used to monitor terpene levels in workplaces such as sawmills. The major advantages with this method are the sampling procedure, which is simple to perform compared to other techniques, the easily automated analysis procedure and the possibility to reuse the samplers.     

CO2 capture and storage from a bioethanol plant: Carbon and energy footprint and economic assessment

Biomass energy and carbon capture and storage (BECCS) can lead to a net removal of atmospheric CO₂. This paper investigates environmental and economic performances of CCS retrofit applied to two mid-sized refineries producing ethanol from sugar beets. Located in the Region Centre France, each refinery has two major CO₂ sources: fermentation and cogeneration units. “carbon and energy footprint” (CEF) and “discounted cash flow” (DCF) analyses show that such a project could be a good opportunity for CCS early deployment. CCS retrofit on fermentation only with natural gas fired cogeneration improves CEF of ethanol production and consumption by 60% without increasing much the non renewable energy consumption. CCS retrofit on fermentation and natural gas fired cogeneration is even more appealing by decreasing of 115% CO₂ emissions, while increasing non renewable energy consumption by 40%. DCF shows that significant project rates of return can be achieved for such small sources if both a stringent carbon policy and direct subsidies corresponding to 25% of necessary investment are assumed. We also underlined that transport and storage cost dilution can be realistically achieved by clustering emissions from various plants located in the same area. On a single plant basis, increasing ethanol production can also produce strong economies of scale.     

Point‐Nonpoint Trading – Can It Work?1

Ribaudo, Marc O. and Jessica Gottlieb, 2011. Point‐Nonpoint Trading – Can It Work? Journal of the American Water Resources Association (JAWRA) 47(1):5‐14. DOI: 10.1111/j.1752‐1688.2010.00454.x Abstract: Water quality trading between point and nonpoint sources is of great interest as an alternative to strict command and control regulations on point sources for achieving water quality goals. The expectation is that trading will reduce the costs of water quality protection, and may speed compliance. The United States Environmental Protection Agency has issued guidance to the States on developing point‐nonpoint trading programs, and United States Department of Agriculture is encouraging farmer participation. However, existing point‐nonpoint trading programs have resulted in very few trades. Supply side and demand side impediments seem to be preventing trades from occurring in most trading programs. These include uncertainty over the number of discharge allowances different management practices can produce, high transactions costs of identifying trading partners, baseline requirements that eliminate low‐cost credits, the reluctance of point sources to trade with unfamiliar agents, and the perception of some farmers that entering contracts with regulated point sources leads to greater scrutiny and potential future regulation. Many of these problems can be addressed through research and program design.     

Novel manure management technologies in no-till and forage introduction to the special series

Surface application of manures leaves nitrogen (N) and phosphorus (P) susceptible to being lost in runoff, and N can also be lost to the atmosphere through ammonia (IH3) volatilization. Tillage immediately after surface application of manure moves manure nutrients under the soil surface, where they are less vulnerable to runoff and volatilization loss. Tillage, however, destroys soil structure, can lead to soil erosion, and is incompatible with forage and no-till systems. A variety of technologies are now available to place manure nutrients under the soil surface, but these are not widely used as surface broadcasting is cheap and long established as the standard method for land application of manure. This collection of papers includes agronomic, environmental, and economic assessments of subsurface manure application technologies, many of which clearly show benefits when comparedwith surface broadcasting. However, there remain significant gaps in our current knowledge, some related to the site-specific nature of technological performance, others related to the nascent and incomplete nature of the assessment process. Thus, while we know that we can improve land application of manure and the sustainability of farming systems with alternatives to surface broadcasting, many questions remain concerning which technologies work best for particular soils, manure types, and farming and cropping systems.     

Using Mediterranean shrubs for the phytoremediation of a soil impacted by pyritic wastes in Southern Spain: a field experiment

Re-vegetation is the main aim of ecological restoration projects, and in Mediterranean environments native plants are desirable to achieve successful restoration. In 1998, the burst of a tailings dam flooded the Guadiamar river valley downstream from Aznalcóllar (Southern Spain) with sludges that contained elevated concentrations of metals and metalloids, polluting soils and waters. A phytoremediation experiment to assess the potential use of native shrub species for the restoration of soils affected by the spillage was performed from 2005 to 2007, with soils divided into two groups: pH < 5 and pH > 5. Four native shrubs (Myrtus communis, Retama sphaerocarpa, Rosmarinus officinalis and Tamarix gallica) were planted and left to grow without intervention. Trace element concentrations in soils and plants, their extractability in soils, transfer factors and plant survival were used to identify the most-interesting species for phytoremediation. Total As was higher in soils with pH < 5. Ammonium sulphate-extractable zinc, copper, cadmium and aluminium concentrations were higher in very-acid soils, but arsenic was extracted more efficiently when soil pH was >5. Unlike As, which was either fixed by Fe oxides or retained as sulphide, the extractable metals showed significant relationships with the corresponding total soil metal concentration and inverse relationships with soil pH. T. gallica, R. officinalis and R. sphaerocarpa survived better in soils with pH > 5, while M. communis had better survival at pH < 5. R. sphaerocarpa showed the highest survival (30%) in all soils. Trace element transfer from soil to harvestable parts was low for all species and elements, and some species may have been able to decrease trace element availability in the soil. Our results suggest that R. sphaerocarpa is an adequate plant species for phytostabilising these soils, although more research is needed to address the self-sustainability of this remediation technique and the associated environmental changes.     

A standardized approach for estimating the permeability of plastic films to soil fumigants under various field and environmental conditions

Minimizing atmospheric emissions of soil fumigants is critical for protecting human and environmental health. Covering the soil surface with a plastic tarp is a common approach to restrict fumigant emissions. The mass transfer of the fumigant vapors through the tarp is often the rate-limiting factor in fumigant emissions. An approach for standardizing measurements of film permeability is proposed that is based on determining the resistance (R) of films to diffusion of fumigants. Using this approach, values were determined for more than 200 film-chemical combinations under a range of temperature, relative humidity, and film handling conditions. Resistance to diffusion was specific for each fumigant/film combination, with the largest range of values observed for the fumigant chloropicrin. For each fumigant, decreased with increasing temperature. Changes in film permeability due to increases in temperature or field installation were generally less than a factor of five. For one film, values determined under conditions of very high relative humidity (approximately 100%) were at least 100 times lower than when humidity was very low (approximately 2%). This approach simplifies the selection of appropriate films for soil fumigation by providing rapid, reproducible, and precise measurements of their permeability to specific fumigants and application conditions.     

Design study of a 150 kWth double loop circulating fluidized bed reactor system for chemical looping combustion with focus on industrial applicability and pressurization

Nowadays the lab scale feasibility of the chemical looping combustion technology has been proved. This article deals with many of the design requirements that need to be fulfilled to make this technology applicable at industrial scale. A design for a 150 kW_th chemical looping combustion reactor system is proposed. In the base case it is supposed to work with gaseous fuels and inexpensive oxygen carriers derived from industrial by-products or natural minerals. More specifically the fuel will be methane and a manganese ore will be the basis for the oxygen carrier. It is a double loop circulating fluidized bed where both the air reactor and the fuel reactor are capable to work in the fast fluidization regime in order to increase the gas solids contact along the reactor body. High operational flexibility is aimed, in this way it will be possible to run with different fuels and oxygen carriers as well as different operating conditions such as variation in air excess. Compactness is a major goal in order to reduce the required solid material and possibly to enclose the reactor body into a pressurized vessel to investigate the chemical looping combustion under pressurized conditions. The mass and heat balance are described, as well as the hydrodynamic investigations performed. Most design solutions presented are taken from industrial standards as one main objective is to meet commercial requirements.     

Ash and deposit formation from oxy-coal combustion in a 100 kW test furnace

Ash deposition is still an unresolved problem when retrofitting existing air-fired coal power plants to oxy-fuel combustion. Experimental data are quite necessary for mechanism validation and model development. This work was designed to obtain laboratory combustor data on ash and deposits from oxy-coal combustion, and to explore the effects of oxy-firing on their formation. Two bituminous coals (Utah coal and Illinois coal) and one sub-bituminous coal (PRB coal) were burned on a down-fired combustor under both oxy- and air-firing. Two oxy-fired cases, i.e., 27 vol% O₂/73 vol% CO₂ and 32 vol% O₂/68 vol% CO₂, were selected to match the radiation flux and the adiabatic flame temperature of air combustion, respectively. Once-through CO₂ was used to simulate fully cleaned recycled flue gas. The flue gas excess oxygen was fixed at 3 vol%. For each case, both size-segregated fly ash and bulk fly ash samples were obtained. Simultaneously, ash deposits were collected on an especially designed un-cooled deposition probe. Ash particle size distributions and chemical composition of all samples were characterized. Data showed that oxy-firing had insignificant impacts on the tri-modal ash particle size distributions and composition size distributions in the size range studied. Bulk ash compositions also showed no significant differences between oxy- and air-firing, except for slightly higher sulfur contents in some oxy-fired ashes. The oxy-fired deposits were thicker than those from air-firing, suggesting enhanced ash deposition rates in oxy-firing. Oxy-firing also had apparent impacts on the deposit composition, especially for those components (e.g., CaO, Fe₂O₃, SO₃, etc.) that could contribute significantly to ash deposition. Based on these results, aerodynamic changes in gas flow and changes in combustion temperature seemed more important than chemical changes of ash particles in determining deposit behavior during oxy-coal combustion.     

C and N Content in Density Fractions of Whole Soil and Soil Size Fraction Under Cacao Agroforestry Systems and Natural Forest in Bahia,Brazil

Agroforestry systems (AFSs) have an important role in capturing above and below ground soil carbon and play a dominant role in mitigation of atmospheric CO₂. Attempts has been made here to identify soil organic matter fractions in the cacao-AFSs that have different susceptibility to microbial decomposition and further represent the basis of understanding soil C dynamics. The objective of this study was to characterize the organic matter density fractions and soil size fractions in soils of two types of cacao agroforestry systems and to compare with an adjacent natural forest in Bahia, Brazil. The land-use systems studied were: (1) a 30-year-old stand of natural forest with cacao (cacao cabruca), (2) a 30-year-old stand of cacao with Erythrina glauca as shade trees (cacao + erythrina), and (3) an adjacent natural forest without cacao. Soil samples were collected from 0-10 cm depth layer in reddish-yellow Oxisols. Soil samples was separated by wet sieving into five fraction-size classes (>2000 μm, 1000–2000 μm, 250–1000 μm, 53–250 μm, and <53 μm). C and N accumulated in to the light (free- and intra-aggregate density fractions) and heavy fractions of whole soil and soil size fraction were determined. Soil size fraction obtained in cacao AFS soils consisted mainly (65 %) of mega-aggregates (>2000 μm) mixed with macroaggregates (32–34%), and microaggregates (1–1.3%). Soil organic carbon (SOC) and total N content increased with increasing soil size fraction in all land-use systems. Organic C-to-total N ratio was higher in the macroaggregate than in the microaggregate. In general, in natural forest and cacao cabruca the contribution of C and N in the light and heavy fractions was similar. However, in cacao + erythrina the heavy fraction was the most common and contributed 67% of C and 63% of N. Finding of this study shows that the majority of C and N in all three systems studied are found in macroaggregates, particularly in the 250–1000 μm size aggregate class. The heavy fraction was the most common organic matter fraction in these soils. Thus, in mature cacao AFS on highly weathered soils the main mechanisms of C stabilization could be the physical protection within macroaggregate structures thereby minimizing the impact of conversion of forest to cacao AFS.