Ammonia volatilization losses from surface-applied urea with urease and nitrification inhibitors

Urease inhibitor (UI) and nitrification inhibitor (NI) have the potential to improve N-use efficiency of applied urea and minimize N losses via gaseous emissions of ammonia (NH 3) to the atmosphere and nitrate (NO3-) leaching into surface and ground water bodies. There is a growing interest in the formulations of coating chemical fertilizers with both UI and NI. However, limited information is available on the combined use of UI and NI applied with urea fertilizer. Therefore the aim of this study was to investigate the effects of treating urea with both UI and NI to minimize NH 3 volatilization. Two experiments were set up in volatilization chambers under controlled conditions to examine this process. In the first experiment, UR was treated with the urease inhibitor NBPT [N-(n-butyl) thiophosphoric acid triamide] at a rate of 1060 mg kg -1 urea and/or with the nitrification inhibitor DCD (dicyandiamide) at rates equivalent to 5 or 10% of the urea N. A randomized experimental design with five treatments and five replicates was used: 1) UR, 2) UR + NBPT, 3) UR + DCD 10%, 4) UR + NBPT + DCD 5%, and 5) UR + NBPT + DCD 10%. The fertilizer treatments were applied to the surface of an acidic Red Latosol soil moistened to 60% of the maximum water retention and placed inside volatilization chambers. Controls chambers were added to allow for NH 3 volatilized from unfertilized soil or contained in the air that swept over the soil surface. The second experiment had an additional treatment with surface-applied DCD. The chambers were glass vessels (1.5 L) fit with air inlet and outlet tubings to allow air to pass over the soil. Ammonia volatilized was swept and carried to a flask containing a boric acid solution to trap the gas and then measured daily by titration with a standardized H 2SO 4 solution. Continuous measurements were recorded for 19 and 23 days for the first and second experiment, respectively. The soil samples were then analyzed for UR-, NH4+-, and NO3--N. Losses of NH 3 by volatilization with unamended UR ranged from 28 to 37% of the applied N, with peak of losses observed the third day after fertilization. NBPT delayed the peak of NH 3 losses due to urease inhibition and reduced NH 3 volatilization between 54 and 78% when compared with untreated UR. Up to 10 days after the fertilizer application, NH 3 losses had not been affected by DCD in the UR or the UR + NBPT treatments; thereafter, NH 3 volatilization tended to decrease, but not when DCD was present. As a consequence, the addition of DCD caused a 5-16% increase in NH 3 volatilization losses of the fertilizer N applied as UR from both the UR and the UR + NBPT treatments. Because the effectiveness of NBPT to inhibit soil urease activity was strong only in the first week, it could be concluded that DCD did not affect the action of NBPT but rather, enhanced volatilization losses by maintaining higher soil NH4+ concentration and pH for a longer time. Depending on the combination of factors influencing NH 3 volatilization, DCD could even offset the beneficial effect of NBPT in reducing NH 3 volatilization losses. © 2012 Elsevier Ltd.

Estudo do comportamento térmico do inseticida HCH com perspectivas para aplicação em descontaminação térmica de solos

Pós-graduação em Química - IBILCE

Uso da oxi-combustão em equipamentos convencionais como alternativa a queima com ar

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Hydrochemistry, water level, and discharge of water from Samoylov Island, Lena Delta, northeastern Siberia, in 2008

Although ponds make up roughly half of the total area of surface water in permafrost landscapes, their relevance to carbon dioxide emissions on a landscape scale has, to date, remained largely unknown. We have therefore investigated the inflows and outflows of dissolved organic and inorganic carbon from lakes, ponds, and outlets on Samoylov Island, in the Lena Delta of northeastern Siberia in September 2008, together with their carbon dioxide emissions. Outgassing of carbon dioxide (CO2) from these ponds and lakes, which cover 25% of Samoylov Island, was found to account for between 74 and 81% of the calculated net landscape-scale CO2 emissions of 0.2-1.1 g C/m**2/d during September 2008, of which 28-43% was from ponds and 27-46% from lakes. The lateral export of dissolved carbon was negligible compared to the gaseous emissions due to the small volumes of runoff. The concentrations of dissolved inorganic carbon in the ponds were found to triple during freezeback, highlighting their importance for temporary carbon storage between the time of carbon production and its emission as CO2. If ponds are ignored the total summer emissions of CO2-C from water bodies of the islands within the entire Lena Delta (0.7-1.3 Tg) are underestimated by between 35 and 62%.

Poluição sonora urbana: a influência de modificações em escapamentos de motocicletas na emissão de ruído

A poluição sonora urbana, em especial a gerada por motocicletas com escapamentos modificados, afeta indistintamente a saúde de toda população de diversas maneiras e tende a aumentar, ao contrário da emissão de gases, que vem se reduzindo ao longo dos anos. Com o objetivo de conter o ruído gerado pelo tráfego urbano, vários países desenvolvem procedimentos, leis e ações mitigatórias como barreiras acústicas e asfaltos fonoabsorventes, porém há grande quantidade de motocicletas, veículo tipicamente de alto potencial de incômodo e ruidoso, que circulam com sistemas de escapamento adulterados e emitem ainda mais excesso de ruído. A inspeção veicular é ferramenta importante no controle de emissões de gases poluentes de veículos em uso, mas falha em restringir aqueles que ultrapassam os limites legais de ruído e, somado a isto, há o agravante de o condutor submeter-se a poluição sonora que ele mesmo produz. A fiscalização de rua surge como alternativa de controle ambiental, mas algumas vezes é contestada por ser subjetiva ou por faltar uma metodologia simples, confiável e eficaz. Buscou-se então compreender a relação entre o aumento do nível sonoro da motocicleta com escapamento modificado ao circular no trânsito e a emissão sonora medida na condição de inspeção, o chamado ruído parado, para trazer subsídios à formação de métodos mais eficazes de fiscalização e controle. Para isto foram avaliadas motocicletas quanto à emissão de ruído em circulação e ruído parado e os resultados obtidos apontam que os escapamentos modificados possuem nível sonoro muito mais elevado que os originais, com forte correspondência entre os dois métodos de medição. Esta poluição sonora atinge de modo particularmente intenso os profissionais, motoboys, que modificam suas motocicletas, pois eles se submetem a todos os fatores que favorecem a perda auditiva por excesso de ruído. Outras questões surgiram em paralelo ao tema principal e foram brevemente avaliadas para se compor o quadro geral, como o nível sonoro de escapamentos não originais avaliados segundo os procedimentos de homologação, a contribuição que a motocicleta traz ao ruído urbano e que resultados estes trazem quanto ao torque e potência da motocicleta. Estes estudos indicaram que a motocicleta modificada contribui fortemente para a poluição sonora urbana, afetando principalmente o condutor e sem trazer ganhos efetivos em termos de potência e dirigibilidade.

Drying of biomass for second generation synfuel production

Drying is a major and challenging step in the pre-treatment of biomass for production of second generation synfuels for transport. The biomass feedstocks are mostly wet and need to be dried from 30 to 60 wt% moisture content to about 10-15 wt%. The present survey aims to define and evaluate a few of the most promising optimised concepts for biomass pre-treatment scheme in the production of second generation synfuels for transport. The most promising commercially available drying processes were reviewed, focusing on the applications, operational factors and emissions of dryers. The most common dryers applied now for biomass in bio-energy plants are direct rotary dryers, but the use of steam drying techniques is increasing. Steam drying systems enable the integration of the dryer to existing energy sources. In addition to integration, emissions and fire or explosion risks have to be considered when selecting a dryer for the plant. In steam drying there will be no gaseous emissions, but the aqueous effluents need often treatment. Concepts for biomass pre-treatment were defined for two different cases including a large-scale wood-based gasification synfuel production and a small-scale pyrolysis process based on wood chips and miscanthus bundles. For the first case a pneumatic conveying steam dryer was suggested. In the second case the flue gas will be used as drying medium in a direct or indirect rotary dryer.

AN EXPERIMENTAL INVESTIGATION INTO THE EFFECTS OF BIODIESEL BLENDS ON PARTICULATE MATTER OXIDATION IN A CATALYZED PARTICULATE FILTER DURING ACTIVE REGENERATION

Active regeneration experiments were carried out on a production 2007 Cummins 8.9L ISL engine and associated DOC and CPF aftertreatment system. The effects of SME biodiesel blends were investigated in this study in order to determine the PM oxidation kinetics associated with active regeneration, and to determine the effect of biodiesel on them. The experimental data from this study will also be used to calibrate the MTU-1D CPF model. Accurately predicting the PM mass retained in the CPF and the oxidation characteristics will provide the basis for computation in the ECU that will minimize the fuel penalty associated with active regeneration. An active regeneration test procedure was developed based on previous experimentation at MTU. During each experiment, the PM mass in the CPF is determined by weighing the filter at various phases. In addition, DOC and CPF pressure drop, particle size distribution, gaseous emissions, temperature, and PM concentration data are collected and recorded throughout each experiment. The experiments covered a range of CPF inlet temperatures using ULSD, B10, and B20 blends of biodiesel. The majority of the tests were performed at CPF PM loading of 2.2 g/L with in-cylinder dosing, although 4.1 g/L and a post-turbo dosing injector were also used. The PM oxidation characteristics at different test conditions were studied in order to determine the effects of biodiesel on PM oxidation during active regeneration. A PM reaction rate calculation method was developed to determine the global activation energy and the corresponding pre-exponential factor for all test fuels. The changing sum of the total flow resistance of the wall, cake, and channels was also determined as part of the data analysis process in order to check on the integrity of the data and to correct input data to be consistent with the expected trends of the resistance based on the engine conditions used in the test procedure. It was determined that increasing the percent biodiesel content in the test fuel tends to increase the PM reaction rate and the regeneration efficiency of fuel dosing, i.e., at a constant CPF inlet temperature, B20 test fuel resulted in the highest PM reaction rate and regeneration efficiency of fuel dosing. Increasing the CPF inlet temperature also increases PM reaction rate and regeneration efficiency of fuel dosing. Performing active regeneration with B20 as opposed to ULSD allows for a lower CPF temperature to be used to reach the same level of regeneration efficiency, or it allows for a shorter regeneration time at a constant CPF temperature, resulting in decreased fuel consumption for the engine during active regeneration in either scenario.

Nitrogen removal and sustainability of vertical flow constructed wetlands for small scale wastewater treatment

The challenge for wastewater professionals is to design and operate treatment processes that support human well being and are environmentally sensitive throughout the life-cycle. This research focuses on one technology for small-scale wastewater treatment: the vertical flow constructed wetland (VFCW), which is herein investigated for the capacity to remove ammonium and nitrate nitrogen from wastewater. Hydraulic regime and presence/absence of vegetation are the basis for a three-phase bench scale experiment to determine oxygen transfer and nitrogen fate in VFCWs. Results show that 90% NH4+-N removal is achieved in aerobic downflow columns, 60% NO3--N removal occurs in anaerobic upflow columns, and 60% removal of total nitrogen can be achieved in downflow-upflow in-series. The experimental results are studied further using a variably saturated flow and reactive transport model, which allows a mechanistic explanation of the fate and transport of oxygen and nitrogen. The model clarifies the mechanisms of oxygen transport and nitrogen consumption, and clarifies the need for readily biodegradable COD for denitrification. A VFCW is then compared to a horizontal flow constructed wetland (HFCW) for life cycle environmental impacts. High areal emissions of greenhouse gases from VFCWs compared to HFCWs are the driver for the study. The assessment shows that because a VFCW is only 25% of the volume of an HFCW designed for the same treatment quality, the VFCW has only 25-30% of HFCW impacts over 12 impact categories and 3 damage categories. Results show that impacts could be reduced by design improvements. Design recommendations are downflow wetlands for nitrification, upflow wetlands for denitrification, series wetlands for total nitrogen removal, hydraulic load of 142 L/m2d, 30 cm downflow wetland depth, 1.0 m upflow wetland depth, recycle, vegetation and medium-grained sand. These improvements will optimize nitrogen removal, minimize gaseous emissions, and reduce wetland material requirements, thus reducing environmental impact without sacrificing wastewater treatment quality.

Dairy cattle-slurry treatment technologies: towards an integrating approach of crop production, animal feeding and environmental impacts

Dairy cattle farms have a well-known environmental impact that affects all ecological compartments: air, soil, water and biosphere [1]. Dairy cattle farming are a significant source of anthropogenic gases from enteric fermentation, manure storage and land application, mainly ammonia (NH3), nitric oxide (NO), nitrous oxide (N2O), carbon dioxide (CO2) and methane (CH4). The emission of such gases represents not only an environmental problem but also leads to energy and nitrogen (N) losses in ruminant production systems [2-5]. Several efforts are required on the development of new technologies and strategies that mitigate gaseous emissions, N losses and improve the efficiency of the energy and N cycles [6, 7]. In the Northwest of Portugal, dairy cattle production has a major impact on the economy, with strong repercussions at national scale. Therefore, our Ph.D. thesis project aims to: a) Study natural supplements as additives in the dairy cattle diet towards a decrease in GHG emissions from feeding operations; b) Compare commercial dairy cattle diets with and without additives on gaseous emissions from manure deposited in a simulated concrete floor; c) Assess the concentrations and emissions of NH3 and greenhouse gases from commercial dairy cattle facilities; d) Evaluate the effects of different additives on lowering gaseous emissions from dairy cattle excreta, using a laboratory system simulating a dairy house concrete floor.

Application of multi-criteria decision making methods to compression ignition engine efficiency and gaseous, particulate and greenhouse gas emissions

Compression ignition (CI) engine design is subject to many constraints which presents a multi-criteria optimisation problem that the engine researcher must solve. In particular, the modern CI engine must not only be efficient, but must also deliver low gaseous, particulate and life cycle greenhouse gas emissions so that its impact on urban air quality, human health, and global warming are minimised. Consequently, this study undertakes a multi-criteria analysis which seeks to identify alternative fuels, injection technologies and combustion strategies that could potentially satisfy these CI engine design constraints. Three datasets are analysed with the Preference Ranking Organization Method for Enrichment Evaluations and Geometrical Analysis for Interactive Aid (PROMETHEE-GAIA) algorithm to explore the impact of 1): an ethanol fumigation system, 2): alternative fuels (20 % biodiesel and synthetic diesel) and alternative injection technologies (mechanical direct injection and common rail injection), and 3): various biodiesel fuels made from 3 feedstocks (i.e. soy, tallow, and canola) tested at several blend percentages (20-100 %) on the resulting emissions and efficiency profile of the various test engines. The results show that moderate ethanol substitutions (~20 % by energy) at moderate load, high percentage soy blends (60-100 %), and alternative fuels (biodiesel and synthetic diesel) provide an efficiency and emissions profile that yields the most “preferred” solutions to this multi-criteria engine design problem. Further research is, however, required to reduce Reactive Oxygen Species (ROS) emissions with alternative fuels, and to deliver technologies that do not significantly reduce the median diameter of particle emissions.

Development of a particle number and particle mass vehicle emissions inventory for an urban fleet

Motor vehicles are major emitters of gaseous and particulate pollution in urban areas, and exposure to particulate pollution can have serious health effects, ranging from respiratory and cardiovascular disease to mortality. Motor vehicle tailpipe particle emissions span a broad size range from 0.003-10µm, and are measured as different subsets of particle mass concentrations or particle number count. However, no comprehensive inventories currently exist in the international published literature covering this wide size range. This paper presents the first published comprehensive inventory of motor vehicle tailpipe particle emissions covering the full size range of particles emitted. The inventory was developed for urban South-East Queensland by combining two techniques from distinctly different disciplines, from aerosol science and transport modelling. A comprehensive set of particle emission factors were combined with traffic modelling, and tailpipe particle emissions were quantified for particle number (ultrafine particles), PM1, PM2.5 and PM10 for light and heavy duty vehicles and buses. A second aim of the paper involved using the data derived in this inventory for scenario analyses, to model the particle emission implications of different proportions of passengers travelling in light duty vehicles and buses in the study region, and to derive an estimate of fleet particle emissions in 2026. It was found that heavy duty vehicles (HDVs) in the study region were major emitters of particulate matter pollution, and although they contributed only around 6% of total regional vehicle kilometres travelled, they contributed more than 50% of the region’s particle number (ultrafine particles) and PM1 emissions. With the freight task in the region predicted to double over the next 20 years, this suggests that HDVs need to be a major focus of mitigation efforts. HDVs dominated particle number (ultrafine particles) and PM1 emissions; and LDV PM2.5 and PM10 emissions. Buses contributed approximately 1-2% of regional particle emissions.

Development of a particle number and particle mass emissions inventory for an urban fleet : a study in South-East Queensland

Motor vehicles are a major source of gaseous and particulate matter pollution in urban areas, particularly of ultrafine sized particles (diameters < 0.1 µm). Exposure to particulate matter has been found to be associated with serious health effects, including respiratory and cardiovascular disease, and mortality. Particle emissions generated by motor vehicles span a very broad size range (from around 0.003-10 µm) and are measured as different subsets of particle mass concentrations or particle number count. However, there exist scientific challenges in analysing and interpreting the large data sets on motor vehicle emission factors, and no understanding is available of the application of different particle metrics as a basis for air quality regulation. To date a comprehensive inventory covering the broad size range of particles emitted by motor vehicles, and which includes particle number, does not exist anywhere in the world. This thesis covers research related to four important and interrelated aspects pertaining to particulate matter generated by motor vehicle fleets. These include the derivation of suitable particle emission factors for use in transport modelling and health impact assessments; quantification of motor vehicle particle emission inventories; investigation of the particle characteristic modality within particle size distributions as a potential for developing air quality regulation; and review and synthesis of current knowledge on ultrafine particles as it relates to motor vehicles; and the application of these aspects to the quantification, control and management of motor vehicle particle emissions. In order to quantify emissions in terms of a comprehensive inventory, which covers the full size range of particles emitted by motor vehicle fleets, it was necessary to derive a suitable set of particle emission factors for different vehicle and road type combinations for particle number, particle volume, PM1, PM2.5 and PM1 (mass concentration of particles with aerodynamic diameters < 1 µm, < 2.5 µm and < 10 µm respectively). The very large data set of emission factors analysed in this study were sourced from measurement studies conducted in developed countries, and hence the derived set of emission factors are suitable for preparing inventories in other urban regions of the developed world. These emission factors are particularly useful for regions with a lack of measurement data to derive emission factors, or where experimental data are available but are of insufficient scope. The comprehensive particle emissions inventory presented in this thesis is the first published inventory of tailpipe particle emissions prepared for a motor vehicle fleet, and included the quantification of particle emissions covering the full size range of particles emitted by vehicles, based on measurement data. The inventory quantified particle emissions measured in terms of particle number and different particle mass size fractions. It was developed for the urban South-East Queensland fleet in Australia, and included testing the particle emission implications of future scenarios for different passenger and freight travel demand. The thesis also presents evidence of the usefulness of examining modality within particle size distributions as a basis for developing air quality regulations; and finds evidence to support the relevance of introducing a new PM1 mass ambient air quality standard for the majority of environments worldwide. The study found that a combination of PM1 and PM10 standards are likely to be a more discerning and suitable set of ambient air quality standards for controlling particles emitted from combustion and mechanically-generated sources, such as motor vehicles, than the current mass standards of PM2.5 and PM10. The study also reviewed and synthesized existing knowledge on ultrafine particles, with a specific focus on those originating from motor vehicles. It found that motor vehicles are significant contributors to both air pollution and ultrafine particles in urban areas, and that a standardized measurement procedure is not currently available for ultrafine particles. The review found discrepancies exist between outcomes of instrumentation used to measure ultrafine particles; that few data is available on ultrafine particle chemistry and composition, long term monitoring; characterization of their spatial and temporal distribution in urban areas; and that no inventories for particle number are available for motor vehicle fleets. This knowledge is critical for epidemiological studies and exposure-response assessment. Conclusions from this review included the recommendation that ultrafine particles in populated urban areas be considered a likely target for future air quality regulation based on particle number, due to their potential impacts on the environment. The research in this PhD thesis successfully integrated the elements needed to quantify and manage motor vehicle fleet emissions, and its novelty relates to the combining of expertise from two distinctly separate disciplines - from aerosol science and transport modelling. The new knowledge and concepts developed in this PhD research provide never before available data and methods which can be used to develop comprehensive, size-resolved inventories of motor vehicle particle emissions, and air quality regulations to control particle emissions to protect the health and well-being of current and future generations.

Nitrous oxide emissions from irrigated cotton soils of northern Australia

An automated gas sampling methodology has been used to estimate nitrous oxide (N2O) emissions from heavy black clay soil in northern Australia where split applications of urea were applied to furrow irrigated cotton. Nitrous oxide emissions from the beds were 643 g N/ha over the 188 day measurement period (after planting), whilst the N2O emissions from the furrows were significantly higher at 967 g N/ha. The DNDC model was used to develop a full season simulation of N2O and N2 emissions. Seasonal N2O emissions were equivalent to 0.83% of applied N, with total gaseous N losses (excluding NH3) estimated to be 16% of the applied N.