Modelling photochemical production of fine particulates in a toluene/NOx/water vapour system

This work investigates the computer modelling of the photochemical formation of smog products such as ozone and aerosol, in a system containing toluene, NOx and water vapour. In particular, the problem of modelling this process in the Commonwealth Scientific and Industrial Research Organization (CSIRO) smog chambers, which utilize outdoor exposure, is addressed. The primary requirement for such modelling is a knowledge of the photolytic rate coefficients. Photolytic rate coefficients of species other than N02 are often related to JNo2 (rate coefficient for the photolysis ofN02) by a simple factor, but for outdoor chambers, this method is prone to error as the diurnal profiles may not be similar in shape. Three methods for the calculation of diurnal JNo2 are investigated. The most suitable method for incorporation into a general model, is found to be one which determines the photolytic rate coefficients for N02, as well as several other species, from actinic flux, absorption cross section and quantum yields. A computer model was developed, based on this method, to calculate in-chamber photolysis rate coefficients for the CSIRO smog chambers, in which ex-chamber rate coefficients are adjusted by accounting for variation in light intensity by transmittance through the Teflon walls, albedo from the chamber floor and radiation attenuation due to clouds. The photochemical formation of secondary aerosol is investigated in a series of toluene-NOx experiments, which were performed in the CSIRO smog chambers. Three stages of aerosol formation, in plots of total particulate volume versus time, are identified: a delay period in which no significant mass of aerosol is formed, a regime of rapid aerosol formation (regime 1) and a second regime of slowed aerosol formation (regime 2). Two models are presented which were developed from the experimental data. One model is empirically based on observations of discrete stages of aerosol formation and readily allows aerosol growth profiles to be calculated. The second model is based on an adaptation of published toluene photooxidation mechanisms and provides some chemical information about the oxidation products. Both models compare favorably against the experimental data. The gross effects of precursor concentrations (toluene, NOx and H20) and ambient conditions (temperature, photolysis rate) on the formation of secondary aerosol are also investigated, primarily using the mechanism model. An increase in [NOx]o results in increased delay time, rate of aerosol formation in regime 1 and volume of aerosol formed in regime 1. This is due to increased formation of dinitrocresol and furanone products. An increase in toluene results in a decrease in the delay time and an increase in the rate of aerosol formation in regime 1, due to enhanced reactivity from the toluene products, such as the radicals from the photolysis of benzaldehyde. Water vapor has very little effect on the formation of aerosol volume, except that rates are slightly increased due to more OH radicals from reaction with 0(1D) from ozone photolysis. Increased temperature results in increased volume of aerosol formed in regime 1 (increased dinitrocresol formation), while increased photolysis rate results in increased rate of aerosol formation in regime 1. Both the rate and volume of aerosol formed in regime 2 are increased by increased temperature or photolysis rate. Both models indicate that the yield of secondary particulates from hydrocarbons (mass concentration aerosol formed/mass concentration hydrocarbon precursor) is proportional to the ratio [NOx]0/[hydrocarbon]0

A study of environmental and management drivers of non-co2 greenhouse gas emissions in Australian agro-ecosystems

Australian climate, soils and agricultural management practices are significantly different from those of the northern hemisphere nations. Consequently, experimental data on greenhouse gas production from European and North American agricultural soils and its interpretation are unlikely to be directly applicable to Australian systems.

Quantifying N2O and CO2 emissions from subtropical pasture

Greenhouse gas emissions from a well established, unfertilized tropical grass-legume pasture were monitored over two consecutive years using high resolution automatic sampling. Nitrous oxide emissions were highest during the summer months and were highly episodic, related more to the size and distribution of rain events than WFPS alone. Mean annual emissions were significantly higher during 2008 (5.7 ± 1.0 g N2O-N/ha/day) than 2007 (3.9 ± 0.4 and g N2O-N/ha/day) despite receiving nearly 500 mm less rain. Mean CO2 (28.2 ± 1.5 kg CO2 C/ha/day) was not significantly different (P < 0.01) between measurement years, emissions being highly dependent on temperature. A negative correlation between CO2 and WFPS at >70% indicated a threshold for soil conditions favouring denitrification. The use of automatic chambers for high resolution greenhouse gas sampling can greatly reduce emission estimation errors associated with temperature and WFPS changes.

Assetti proprietari e meccanismi di governance nelle imprese familiari [Finacial reporting in small family firms : searching for a new framework]

SOMMARIO: 1. La “governance” nelle aziende familiari: rilevanza, aspetti distintivi e criticità. 2. Il ruolo della compagine proprietaria nella definizione dei meccanismi di governo. 3. Composizione e funzioni del consiglio d’amministrazione. 4. I patti di famiglia come strumento di disciplina dei rapporti impresa-famiglia. 5. Considerazioni conclusive: prospettive di analisi e scenari futuri negli studi sulla governance delle imprese familiari.

L'informativa di bilancio nelle imprese familiari di piccole dimensioni : caratteri distintivi e aspetti evolutivi

SOMMARIO: 1. I fattori che incidono sulla funzione informativa del bilancio nelle imprese familiari. 2. Funzione, obiettivi e attese informative nella comunicazione esterna delle imprese familiari. 3. I caratteri del “familismo” nei prospetti di bilancio. 4. Verso un nuovo modello di bilancio per le imprese familiari: riflessioni critiche e spunti per la ricerca.

Reduction of environmental effects of civil aircraft through multi-objective flight plan optimisation

With rising environmental alarm, the reduction of critical aircraft emissions including carbon dioxides (CO2) and nitrogen oxides (NOx) is one of most important aeronautical problems. There can be many possible attempts to solve such problem by designing new wing/aircraft shape, new efficient engine, etc. The paper rather provides a set of acceptable flight plans as a first step besides replacing current aircrafts. The paper investigates a green aircraft design optimisation in terms of aircraft range, mission fuel weight (CO2) and NOx using advanced Evolutionary Algorithms coupled to flight optimisation system software. Two multi-objective design optimisations are conducted to find the best set of flight plans for current aircrafts considering discretised altitude and Mach numbers without designing aircraft shape and engine types. The objectives of first optimisation are to maximise range of aircraft while minimising NOx with constant mission fuel weight. The second optimisation considers minimisation of mission fuel weight and NOx with fixed aircraft range. Numerical results show that the method is able to capture a set of useful trade-offs that reduce NOx and CO2 (minimum mission fuel weight).

Raman spectroscopy of hydrogene-arsenate group (AsO3OH) in solid-state compounds: cobalt mineral phase burgessite Co2(H2O)4[AsO3OH]2•H2O

Raman spectrum of burgessite, Co2(H2O)4[AsO3OH]2.H2O was studied, interpreted and compared with its infrared spectrum. The stretching and bending vibrations of (AsO3) and As-OH units together with the stretching, bending and libration modes of water molecules and hydroxyl ions were assigned. The range of O-H...O hydrogen bond lengths was inferred from the Raman and infrared spectra of burgessite. The presence of (AsO3OH)2- units in the crystal structure of burgessite was proved in agreement with its recently solved crystal structure. Raman and infrared spectra of erythrite inferred from the RRUFF database are used for comparison.

An infrared study of adsorption of paranitrophenol on mono, di and trialkyl surfactant intercalated organoclays

Infrared spectroscopy has been used to study the adsorption of paranitrophenol on mono, di and tri alkyl surfactant intercalated montmorillonite. Organoclays were obtained by the cationic exchange of mono, di and tri alkyl chain surfactants for sodium ions [hexadecyltrimethylammonium bromide (HDTMAB), dimethyldioctadecylammonium bromide (DDOAB), methyltrioctadecylammonium bromide (MTOAB)] in an aqueous solution with Na-montmorillonite. Upon formation of the organoclay, the properties change from strongly hydrophilic to strongly hydrophobic. This change in surface properties is observed by a decrease in intensity of the OH stretching vibrations assigned to water in the cation hydration sphere of the montmorillonite. As the cation is replaced by the surfactant molecules the paranitrophenol replaces the surfactant molecules in the clay interlayer. Bands attributed to CH stretching and bending vibrations change for the surfactant intercalated montmorillonite. Strong changes occur in the HCH deformation modes of the methyl groups of the surfactant. These changes are attributed to the methyl groups locking into the siloxane surface of the montmorillonite. Such a concept is supported by changes in the SiO stretching bands of the montmorillonite siloxane surface. This study demonstrates that paranitrophenol will penetrate into the untreated clay interlayer and replace the intercalated surfactant in surfactant modified clay, resulting in the change of the arrangement of the intercalated surfactant.

How can soil monitoring networks be used to improve predictions of organic carbon pool dynamics and CO2 fluxes in agricultural soils?

Abstract As regional and continental carbon balances of terrestrial ecosystems become available, it becomes clear that the soils are the largest source of uncertainty. Repeated inventories of soil organic carbon (SOC) organized in soil monitoring networks (SMN) are being implemented in a number of countries. This paper reviews the concepts and design of SMNs in ten countries, and discusses the contribution of such networks to reducing the uncertainty of soil carbon balances. Some SMNs are designed to estimate country-specific land use or management effects on SOC stocks, while others collect soil carbon and ancillary data to provide a nationally consistent assessment of soil carbon condition across the major land-use/soil type combinations. The former use a single sampling campaign of paired sites, while for the latter both systematic (usually grid based) and stratified repeated sampling campaigns (5–10 years interval) are used with densities of one site per 10–1,040 km². For paired sites, multiple samples at each site are taken in order to allow statistical analysis, while for the single sites, composite samples are taken. In both cases, fixed depth increments together with samples for bulk density and stone content are recommended. Samples should be archived to allow for re-measurement purposes using updated techniques. Information on land management, and where possible, land use history should be systematically recorded for each site. A case study of the agricultural frontier in Brazil is presented in which land use effect factors are calculated in order to quantify the CO2 fluxes from national land use/management conversion matrices. Process-based SOC models can be run for the individual points of the SMN, provided detailed land management records are available. These studies are still rare, as most SMNs have been implemented recently or are in progress. Examples from the USA and Belgium show that uncertainties in SOC change range from 1.6–6.5 Mg C ha−1 for the prediction of SOC stock changes on individual sites to 11.72 Mg C ha−1 or 34% of the median SOC change for soil/land use/climate units. For national SOC monitoring, stratified sampling sites appears to be the most straightforward attribution of SOC values to units with similar soil/land use/climate conditions (i.e. a spatially implicit upscaling approach). Keywords Soil monitoring networks - Soil organic carbon - Modeling - Sampling design

Influence of biochars on flux of N2O and CO2 from Ferrosol

Biochars produced by slow pyrolysis of greenwaste (GW), poultry litter (PL), papermill waste (PS), and biosolids (BS) were shown to reduce N₂O emissions from an acidic Ferrosol. Similar reductions were observed for the untreated GW feedstock. Soil was amended with biochar or feedstock giving application rates of 1 and 5%. Following an initial incubation, nitrogen (N) was added at 165 kg/ha as urea. Microcosms were again incubated before being brought to 100% water-filled porosity and held at this water content for a further 47 days. The flooding phase accounted for the majority (<80%) of total N₂O emissions. The control soil released 3165 mg N₂O-N/m², or 15.1% of the available N as N₂O. Amendment with 1 and 5% GW feedstock significantly reduced emissions to 1470 and 636 mg N₂O-N/m², respectively. This was equivalent to 8.6 and 3.8% of applied N. The GW biochar produced at 350°C was least effective in reducing emissions, resulting in 1625 and 1705 mg N₂O-N/m² for 1 and 5% amendments. Amendment with BS biochar at 5% had the greatest impact, reducing emissions to 518 mg N₂O-N/m², or 2.2% of the applied N over the incubation period. Metabolic activity as measured by CO₂ production could not explain the differences in N₂O emissions between controls and amendments, nor could NH₄⁺ or NO₃^– concentrations in biochar-amended soils. A decrease in NH₄⁺ and NO₃^– following GW feedstock application is likely to have been responsible for reducing N₂O emissions from this amendment. Reduction in N₂O emissions from the biochar-amended soils was attributed to increased adsorption of NO₃^–. Small reductions are possible due to improved aeration and porosity leading to lower levels of denitrification and N₂O emissions. Alternatively, increased pH was observed, which can drive denitrification through to dinitrogen during soil flooding.

Poly[di-mu-aqua-bis(mu-2-amino-4-nitrobenzoato)dicaesium]

In the structure of title compound [Cs2(C7H5N2O4)2(H2O)2]n the asymmetric unit comprises two independent and different Cs centres, one nine-coordinate, the other seven coordinate, with both having irregular stereochemistry. The CsO9 coordination comprises oxygen donors from three bridging water molecules, one of which is doubly bridging, three from carboxylate groups, and three from nitro groups, of which two are bidentate chelate bridging. The CsO6N coordination comprises the two bridging water molecules, one amine N donor, one carboxyl O donor and four O donors from nitro groups (two from the chelate bridges). The extension of the dimeric unit gives a two-dimensional polymeric structure which is stabilized by both intra- and intermolecular amine N-H...O and water O-H...O hydrogen bonds to carboxyl O acceptors, as well as inter-ring pi-pi interactions [minimum ring centroid separation, 3.4172(15)A].

Are low CO2 emitters in rural areas also socially excluded? An empirical investigation of travel diary data from rural Northern Ireland

The reduction of CO2 emissions and social exclusion are two key elements of UK transport strategy. Despite intensive research on each theme, little effort has so far been made linking the relationship between emissions and social exclusion. In addition, current knowledge on each theme is limited to urban areas; little research is available on these themes for rural areas. This research contributes to this gap in the literature by analysing 157 weekly activity-travel diary data collected from three case study areas with differential levels of area accessibility and area mobility options, located in rural Northern Ireland. Individual weekly CO2 emission levels from personal travel diaries (both hot exhaust emission and cold-start emission) were calculated using average speed models for different modes of transport. The socio-spatial patterns associated with CO2 emissions were identified using a general linear model whereas binary logistic regression analyses were conducted to identify mode choice behaviour and activity patterns. This research found groups that emitted a significantly lower level of CO2 included individuals living in an area with a higher level of accessibility and mobility, non-car, non-working, and low-income older people. However, evidence in this research also shows that although certain groups (e.g. those working, and residing in an area with a lower level of accessibility) emitted higher levels of CO2, their rate of participation in activities was however found to be significantly lower compared to their counterparts. Based on the study findings, this research highlights the need for both soft (e.g. teleworking) and physical (e.g. accessibility planning) policy measures in rural areas in order to meet government’s stated CO2 reduction targets while at the same time enhancing social inclusion.

[P,P-Di-tert-butyl-N-trimethylsilyl- P-(trimethylsilylamino)phosphineimidato-N,N]bis(pyridine-N)- lithium(I)

In the title compound, [Li(C14H36N2PSi2)(C5H5N)2], the bulky chelating monoanionic P,P-di-tert-butyl-N-trimethylsilyl-P-(trimethylsilylamino)phosphine imidate ligand and two pyridine ligands bind to Li in a pseudo-tetrahedral arrangement with twofold symmetry. The Li-N [phosphine]distance is 2.048 (5) Å, while the LiP distance is 2.520 (6) Å

Aircraft emission reduction through multi-disciplinary flight path optimisation

There is worldwide interest in reducing aircraft emissions. The difficulty of reducing emissions including water vapour, carbon dioxide (CO2) and oxides of nitrogen (NOx) is mainly due from the fact that a commercial aircraft is usually designed for a particular optimal cruise altitude but may be requested or required to operate and deviate at different altitude and speeds to archive a desired or commanded flight plan, resulting in increased emissions. This is a multi- disciplinary problem with multiple trade-offs such as optimising engine efficiency, minimising fuel burnt, minimise emissions while maintaining aircraft separation and air safety. This project presents the coupling of an advanced optimisation technique with mathematical models and algorithms for aircraft emission reduction through flight optimisation. Numerical results show that the method is able to capture a set of useful trade-offs between aircraft range and NOx, and mission fuel consumption and NOx. In addition, alternative cruise operating conditions including Mach and altitude that produce minimum NOx and CO2 (minimum mission fuel weight) are suggested.