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

Real-time performance modelling of a sustained attention to response task

Vigilance declines when exposed to highly predictable and uneventful tasks. Monotonous tasks provide little cognitive and motor stimulation and contribute to human errors. This paper aims to model and detect vigilance decline in real time through participant’s reaction times during a monotonous task. A lab-based experiment adapting the Sustained Attention to Response Task (SART) is conducted to quantify the effect of monotony on overall performance. Then relevant parameters are used to build a model detecting hypovigilance throughout the experiment. The accuracy of different mathematical models are compared to detect in real-time – minute by minute - the lapses in vigilance during the task. We show that monotonous tasks can lead to an average decline in performance of 45%. Furthermore, vigilance modelling enables to detect vigilance decline through reaction times with an accuracy of 72% and a 29% false alarm rate. Bayesian models are identified as a better model to detect lapses in vigilance as compared to Neural Networks and Generalised Linear Mixed Models. This modelling could be used as a framework to detect vigilance decline of any human performing monotonous tasks.

Wheat Production Systems And Global Climate Change

About this book: Over 100 authors present 25 contributions on the impacts of global change on terrestrial ecosystems including:key processes of the earth system such as the CO2 fertilization effect, shifts in disturbances and biome distribution, the saturation of the terrestrial carbon sink, and changes in functional biodiversity,ecosystem services such the production of wheat, pest control, and carbon storage in croplands, and sensitive regions in the world threaten by rapid changes in climate and land use such as high latitudes ecosystems, tropical forest in Southeast Asia, and ecosystems dominated by Monsoon climate.The book also explores new research developments on spatial thresholds and nonlinearities, the key role of urban development in global biogeochemical processes, and the integration of natural and social sciences to address complex problems of the human-environment system.

Nitrogen fertilizer management for nitrous oxide (N2O) mitigation in intensive corn (Maize) production: an emissions reduction protocol for US Midwest agriculture

Nitrous oxide (N2O) is a major greenhouse gas (GHG) product of intensive agriculture. Fertilizer nitrogen (N) rate is the best single predictor of N2O emissions in row-crop agriculture in the US Midwest. We use this relationship to propose a transparent, scientifically robust protocol that can be utilized by developers of agricultural offset projects for generating fungible GHG emission reduction credits for the emerging US carbon cap and trade market. By coupling predicted N2O flux with the recently developed maximum return to N (MRTN) approach for determining economically profitable N input rates for optimized crop yield, we provide the basis for incentivizing N2O reductions without affecting yields. The protocol, if widely adopted, could reduce N2O from fertilized row-crop agriculture by more than 50%. Although other management and environmental factors can influence N2O emissions, fertilizer N rate can be viewed as a single unambiguous proxy—a transparent, tangible, and readily manageable commodity. Our protocol addresses baseline establishment, additionality, permanence, variability, and leakage, and provides for producers and other stakeholders the economic and environmental incentives necessary for adoption of agricultural N2O reduction offset projects.

Constraints of nutrient availability on primary production in two alpine tundra communities

A nutrient amendment experiment was conducted for two growing seasons in two alpine tundra communities to test the hypotheses that: (1) primary production is limited by nutrient availability, and (2) physiological and developmental constraints act to limit the responses of plants from a nutrient-poor community more than plants from a more nutrient-rich community to increases in nutrient availability. Experimental treatments consisted of N, P, and N+P amendments applied to plots in two physiognomically similar communities, dry and wet meadows. Extractable N and P from soils in nonfertilized control plots indicated that the wet meadow had higher N and P availability. Photosynthetic, nutrient uptake, and growth responses of the dominants in the two communities showed little difference in the relative capacity of these plants to respond to the nutrient additions. Aboveground production responses of the communities to the treatments indicated N availability was limiting to production in the dry meadow community while N and P availability colimited production in the wet meadow community. There was a greater production response to the N and N+P amendments in the dry meadow relative to the wet meadow, despite equivalent functional responses of the dominant species of both communities. The greater production response in the dry meadow was in part related to changes in community structure, with an increase in the proportion of graminoid and forb biomass, and a decrease in the proportion of community biomass made up by the dominant sedge Kobresia myosuroides. Species richness increased significantly in response to the N+P treatment in the dry meadow. Graminoid biomass increased significantly in the wet meadow N and N+P plots, while forb biomass decreased significantly, suggesting a competitive interaction for light. Thus, the difference in community response to nutrient amendments was not the result of functional changes at the leaf level of the dominant species, but rather was related to changes in community structure in the dry meadow, and to a shift from a nutrient to a light limitation of production in the wet meadow.

Cell interactions of osteoarthritic subchondral bone osteoblasts and articular chondrocytes aggravate MMP-2 and MMP-9 production through the mediation of ERK1/2 and JNK phosphorylation

Matrix Metalloproteinases (MMP) play a key role in osteoarthritis (OA) development. The aim of the present study was to investigate whether, the cross-talk between subchondral bone osteoblasts (SBOs) and articular cartilage chondrocytes (ACCs) in OA alters the expression and regulation of MMPs, and also to test the potential involvement of mitogen activated protein kinase (MAPK) signalling pathway during this process.

Sustained convergence, axial length, and corneal topography

Purpose: To investigate the influence of convergence on axial length and corneal topography in young adult subjects.---------- Methods: Fifteen emmetropic young adult subjects with normal binocular vision had axial length and corneal topography measured immediately before and after a 15-min period of base out (BO) prismatic spectacle lens wear. Two different magnitude prismatic spectacles were worn in turn (8 [DELTA] BO and 16 [DELTA] BO), and for both tasks, distance fixation was maintained for the duration of lens wear. Eight subjects returned on a separate day for further testing and had axial length measured before, during, and immediately after a 15-min convergence task.---------- Results: No significant change was found to occur in axial length either during or after the sustained convergence tasks (p > 0.6). Some small but significant changes in corneal topography were found to occur after sustained convergence. The most significant corneal change was observed after the 16 [DELTA] BO prism wear. The corneal refractive power spherocylinder power vector J0 was found to change by a small (mean change of 0.03 D after the 16 [DELTA] BO task) but statistically significant (p = 0.03) amount as a result of the convergence task (indicative of a reduction in with-the-rule corneal astigmatism after convergence). Corneal axial power was found to exhibit a significant flattening in superior regions. Conclusions: Axial length appears largely unchanged by a period of sustained convergence. However, small but significant changes occur in the topography of the cornea after convergence.

Making space and place for knowledge production : socio-spatial development of knowledge community precincts

In the knowledge era the importance of making space and place for knowledge production is clearly understood worldwide by many city administrations that are keen on restructuring their cities as highly competitive and creative places. Consequently, knowledge-based urban development and socio-spatial development of knowledge community precincts have taken their places among the emerging agendas of the urban planning and development practice. This chapter explores these emerging issues and scrutinizes the development of knowledge community precincts that have important economic, social and cultural dimensions on the formation of competitive and creative urban regions. The chapter also sheds light on the new challenges for planning discipline, and discusses the need for and some specifics of a new planning paradigm suitable for dealing with 21st Century’s socio-economic development and urbanization problems.

What learners "know" through digital media production : learning by design

The power to influence others in ever-expanding social networks in the new knowledge economy is tied to capabilities with digital media production that require increased technological knowledge. This article draws on research in elementary classrooms to examine the repertoires of cross-disciplinary knowledge that literacy learners need to produce innovative digital media via the “social web”. The article builds on Learning by Design and the Knowledge Processes to describe “how” learning occurs, while presenting a model to theorise “what” students know – the Knowledge Assets – when learners produce digital and multimodal texts.

Three-dimensional hydrogen-bonded structures in the guanidinium salts of the monocyclic dicarboxylic acids rac-trans-cyclohexane-1,2-dicarboxylic acid (2:1, anhydrous), isophthalic acid (1:1, monohydrate) and terephthalic acid (2:1, trihydrate).

The structures of bis(guanidinium)rac-trans-cyclohexane-1,2-dicarboxylate, 2(CH6N3+) C8H10O4- (I), guanidinium 3-carboxybenzoate monohydrate CH6N3+ C8H5O4- . H2O (II) and bis(guanidinium) benzene-1,4-dicarboxylate trihydrate, 2(CH6N3+) C8H4O4^2- . 3H2O (III) have been determined and the hydrogen bonding in each examined. All three compounds form three-dimensional hydrogen-bonded framework structures. In anhydrous (I), both guanidinium cations give classic cyclic R2/2(8) N--H...O,O'(carboxyl) and asymmetric cyclic R1/2(6) hydrogen-bonding interactions while one cation gives an unusual enlarged cyclic interaction with O acceptors of separate ortho-related carboxyl groups [graph set R2/2(11)]. Cations and anions also associate across inversion centres giving cyclic R2/4(8) motifs. In the 1:1 guanidinium salt (II), the cation gives two separate cyclic R1/2(6) interactions, one with a carboxyl O-acceptor, the other with the water molecule of solvation. The structure is unusual in that both carboxyl groups give short inter-anion O...H...O contacts, one across a crystallographic inversion centre [2.483(2)\%A], the other about a two-fold axis of rotation [2.462(2)\%A] with a half-occupancy hydrogen delocalized on the symmetry element in each. The water molecule links the cation--anion ribbon structures into a three-dimensional framework. In (III), the repeating molecular unit comprises a benzene-1,4-dicarboxylate dianion which lies across a crystallographic inversion centre, two guanidinium cations and two water molecules of solvation (each set related by two-fold rotational symmetry), and a single water molecule which lies on a two-fold axis. Each guanidinium cation gives three types of cyclic interactions with the dianions: one R^1^~2~(6), the others R2/3(8) and R3/3(10) (both of these involving the water molecules), giving a three-dimensional structure through bridges down the b cell direction. The water molecule at the general site also forms an unusual cyclic R2/2(4) homodimeric association across an inversion centre [O--H...O, 2.875(2)\%A]. The work described here provides further examples of the common cyclic guanidinium cation...carboxylate anion hydrogen-bonding associations as well as featuring other less common cyclic motifs.

Hydrogen bonding in the anhydrous 1:1 proton-transfer compounds of isonipecotamide with nitro-substituted benzoic acids: the salts of the three isomeric mononitrobenzoic acids and of 3,5-dinitrobenzoic acid

The structures of the anhydrous 1:1 proton-transfer compounds of isonipecotamide (piperidine-4-carboxamide) with the three isomeric mononitro-substituted benzoic acids and 3,5-dinitrobenzoic acid, namely 4-carbamoylpiperidinium 2-nitrobenzoate (I), 4-carbamoylpiperidinium 3-nitrobenzoate (II), 4-carbamoylpiperidinium 4-nitrobenzoate (III), (C6H13N2O+ C7H4NO4-) and 4-carbamoylpiperidinium 3,5-dinitrobenzoate (IV) (C6H13N2O+ C7H5N2O6-)respectively, have been determined at 200 K. All salts form hydrogen-bonded structures: three-dimensional in (I), two-dimensional in (II) and (III) and one-dimensional in (IV). Featured in the hydrogen bonding of three of these [(I), (II) and (IV)] is the cyclic head-to-head amide--amide homodimer motif [graph set R2/2~(8)] through a duplex N---H...O association, the dimer then giving structure extension via either piperidinium or amide H-donors and carboxylate-O and in some examples [(II) and (IV)], nitro-O atom acceptors. In (I), the centrosymmetric amide-amide homodimers are expanded laterally through N-H...O hydrogen bonds via cyclic R2/4(8) interactions forming ribbons which extend along the c cell direction. These ribbons incorporate the 2-nitrobenzoate cations through centrosymmetric cyclic piperidine N-H...O(carboxyl) associations [graph set R4/4(12)], giving inter-connected sheets in the three-dimensional structure. In (II) in which no amide-amide homodimer is present, duplex piperidinium N-H...O(amide) hydrogen-bonding homomolecular associations [graph set R2/2(14)] give centrosymmetric head-to-tail dimers. Structure extension occurs through hydrogen-bonding associations between both the amide H-donors and carboxyl and nitro O-acceptors as well as a three-centre piperidinium N-H...O,O'(carboxyl) cyclic R2/1(4) association giving the two-dimensional network structure. In (III), the centrosymmetric amide-amide dimers are linked through the two carboxyl O-atom acceptors of the anions via bridging piperidinium and amide N-H...O,O'...H-N(amide) hydrogen bonds giving the two-dimensional sheet structure which features centrosymmetric cyclic R4/4(12) associations. In (IV), the amide-amide dimer is also centrosymmetric with the dimers linked to the anions through amide N-H...O(nitro) interactions. The piperidinium groups extend the structure into one-dimensional ribbons via N-H...O(carboxyl) hydrogen bonds. The structures reported here further demonstrate the utility of the isonipecotamide cation in molecular assembly and highlight the efficacy of the cyclic R2/2(8) amide-amide hydrogen-bonding homodimer motif in this process and provide an additional homodimer motif type in the head-to-tail R2/2(14) association.

iPed : pedagogy for digital text production

Reading and writing are being transformed by global changes in communication practices using new media technologies. This paper introduces iPed, a research-based pedagogy that enables teachers to navigate innovative digital text production in the literacy classroom. The pedagogy was generated in the context of a longitudinal digital literacy intervention in a school that services low-socioeconomic and ethnically diverse students. iPed synthesizes four key pedagogies that were salient in the analysis of over 180 hours of lesson observations – Link, Challenge, Co-Create, and Share. The strengths of the pedagogy include connecting to students’ home cultures, critical media literacy, collaborative and creative digital text production, and gaining cosmopolitan recognition within global communities.