Volume-based size distribution of accumulation and coarse particles (PM0.1–10) from cooking fume during oil heating

Particulate matter generated during the cooking process has been identified as one of the major problems of indoor air quality and indoor environmental health. Reliable assessment of exposure to cooking-generated particles requires accurate information of emission characteristics especially the size distribution. This study characterizes the volume/mass-based size distribution of the fume particles at the oil-heating stage for the typical Chinese-style cooking in a laboratory kitchen. A laser-diffraction size analyzer is applied to measure the volume frequency of fume particles ranged from 0.1 to 10 μm, which contribute to most mass proportion in PM2.5 and PM10. Measurements show that particle emissions have little dependence on the types of vegetable oil used but have a close relationship with the heating temperature. It is found that volume frequency of fume particles in the range of 1.0–4.0 μm accounts for nearly 100% of PM0.1–10 with the mode diameter 2.7 μm, median diameter 2.6 μm, Sauter mean diameter 3.0 μm, DeBroukere mean diameter 3.2 μm, and distribution span 0.48. Such information on emission characteristics obtained in this study can be possibly used to improve the assessment of indoor air quality due to PM0.1–10 in the kitchen and residential flat.

Structural variations in self-assembled coordination complexes of Zn(II) with hexamethylenetetramine and isomeric 2-, 3- and 4-nitrobenzoates

Three new zinc(II)-hexamethylenetetramine (hmt) complexes [Zn-2(4-nbz)(4)(mu(2)-hmt)(OH2)(hmt)] (1). [Zn-2(2-nbz)(4)(mu(2)-hmt)(2)](n) (2) and [Zn-3(3-nbz)(4)(mu(2)-hmt)(mu(2)-OH)(mu(3)-OH)](n) (3) with three isomeric nitrobenzoate, [4-nbz = 4-nitrobenzoate, 2-nbz = 2-nitrobenzoate and 3-nbz = 3-nitrobenzoate] have been synthesized and structurally characterized by X-ray crystallography. Their identities have also been established by elemental analysis: IR, NMR, UV-Vis and mass spectral studies. 1 is a dinuclear complex formed by bridging hmt with mu(2) coordinating mode. The geometry around the Zn centers in 1 is distorted tetrahedral. Paddle-wheel centrosymmetric Zn-2(2-nbz)(4) units of complex 2 are interconnected by mu(2)-hmt forming a one-dimensional chain with square-pyramidal geometries around the Zn centers. Compound 3 contains a mu(2)/mu(3)-hydroxido and mu(2)-hmt bridged 1D chain. In this complex, varied geometries around the Zn centers are observed viz, tetrahedral, square pyramidal and trigonal bipyramidal. Various weak forces, i.e. lone pair-pi, pi-pi and CH-pi interactions, play a key role in stabilizing the observed structures for complexes 1,2 and 3. This series of complexes demonstrates that although the nitro group does not coordinate to the metal center, its presence at the 2-, 3- or 4-position of the phenyl ring has a striking effect on the dimensionality as well as the structure of the resulted coordination polymers, probably due to the participation of the nitro group in 1.p.center dot center dot center dot pi and/or C-H center dot center dot center dot pi interactions.

Host–guest supramolecular interactions in the coordination compounds of 4,4′-azobis(pyridine) with MnX2(X = NCS–, NCNCN–, and PF6–): structural analyses and theoretical study

Three new Mn(II) coordination compounds {[Mn(NCNCN)2(azpy)]·0.5azpy}n (1), {[Mn(NCS)2(azpy)(CH3OH)2]·azpy}n (2), and [Mn(azpy)2(H2O)4][Mn(azpy)(H2O)5]·4PF6·H2O·5.5azpy (3) (where azpy = 4,4'-azobis-(pyridine)) have been synthesized by self-assembly of the primary ligands, dicyanamide, thiocyanate, and hexafluorophosphate, respectively, together with azpy as the secondary spacer. All three complexes were characterized by elemental analyses, IR spectroscopy, thermal analyses, and single crystal X-ray crystallography. The structural analyses reveal that complex 1 forms a two-dimensional (2D) grid sheet motif These sheets assemble to form a microporous framework that incorporates coordination-free azpy by host-guest pi center dot center dot center dot pi. and C-H center dot center dot center dot N hydrogen bonding interactions. Complex 2 features azpy bridged one-dimensional (ID) chains of centrosymmetric [Mn(NCS)(2)(CH3OH)(2)} units which form a 2D porous sheet via a CH3 center dot center dot center dot pi supramolecular interaction. A guest azpy molecule is incorporated within the pores by strong H-bonding interactions. Complex 3 affords a 0-D motif with two monomeric Mn(II) units in the asymmetric unit. There exist pi center dot center dot center dot pi, anion center dot center dot center dot pi, and strong hydrogen bonding interactions between the azpy, water, and the anions. Density functional theory (DFT) calculations, at the M06/6-31+G* level of theory, are used to characterize a great variety of interactions that explicitly show the importance of host-guest supramolecular interactions for the stabilization of coordination compounds and creation of the fascinating three-dimensional (3D) architecture of the title compounds.

A very rare self-assembled ribbon of fused cyclic water pentamers encapsulated in a Cu-II based metal-organic framework

A metal organic framework of Cu-II, tartarate (tar) and 2,2'-bipyridyl (2,2'-bipy)], {[Cu(tar)(2,2'-bipy)]center dot 5H(2)O}(n)} (1) has been synthesized at the mild ambient condition and characterized by single crystal X-ray crystallography. In the compound, the Cu(2,2'-bipy) entities are bridged by tartarate ions which are coordinated to Cu-II by both hydroxyl and monodentate carboxylate oxygen to form a one-dimensional chain. The non-coordinated water molecules form ID water chains by edge-sharing cyclic water pentamers along with dangling water dimers. It shows reversible water expulsion upon heating. The water chains join the ID coordination polymeric chains to a 31) network through hydrogen-bond interactions.

Adaptation-induced collective dynamics of a single-cell protozoan

We investigate the behavior of a single-cell protozoan in a narrow tubular ring. This environment forces them to swim under a one-dimensional periodic boundary condition. Above a critical density, single-cell protozoa aggregate spontaneously without external stimulation. The high-density zone of swimming cells exhibits a characteristic collective dynamics including translation and boundary fluctuation. We analyzed the velocity distribution and turn rate of swimming cells and found that the regulation of the turing rate leads to a stable aggregation and that acceleration of velocity triggers instability of aggregation. These two opposing effects may help to explain the spontaneous dynamics of collective behavior. We also propose a stochastic model for the mechanism underlying the collective behavior of swimming cells.

Groundwater residence time distributions in peatlands: implications for peat decomposition and accumulation

Peat soils consist of poorly decomposed plant detritus, preserved by low decay rates, and deep peat deposits are globally significant stores in the carbon cycle. High water tables and low soil temperatures are commonly held to be the primary reasons for low peat decay rates. However, recent studies suggest a thermodynamic limit to peat decay, whereby the slow turnover of peat soil pore water may lead to high concentrations of phenols and dissolved inorganic carbon. In sufficient concentrations, these chemicals may slow or even halt microbial respiration, providing a negative feedback to peat decay. We document the analysis of a simple, one-dimensional theoretical model of peatland pore water residence time distributions (RTDs). The model suggests that broader, thicker peatlands may be more resilient to rapid decay caused by climate change because of slow pore water turnover in deep layers. Even shallow peat deposits may also be resilient to rapid decay if rainfall rates are low. However, the model suggests that even thick peatlands may be vulnerable to rapid decay under prolonged high rainfall rates, which may act to flush pore water with fresh rainwater. We also used the model to illustrate a particular limitation of the diplotelmic (i.e., acrotelm and catotelm) model of peatland structure. Model peatlands of contrasting hydraulic structure exhibited identical water tables but contrasting RTDs. These scenarios would be treated identically by diplotelmic models, although the thermodynamic limit suggests contrasting decay regimes. We therefore conclude that the diplotelmic model be discarded in favor of model schemes that consider continuous variation in peat properties and processes.

Structural and magnetic studies of Schiff base complexes of nickel(ii) nitrite: change in crystalline state, ligand rearrangement and a very rare μ-nitrito-1κO:2κN:3κO′ bridging mode

Four new nickel(II) complexes, [Ni2L2(NO2)2]·CH2Cl2·C2H5OH, 2H2O (1), [Ni2L2(DMF)2(m-NO2)]ClO4·DMF (2a), [Ni2L2(DMF)2(m-NO2)]ClO4 (2b) and [Ni3L¢2(m3-NO2)2(CH2Cl2)]n·1.5H2O (3) where HL = 2-[(3-amino-propylimino)-methyl]-phenol, H2L¢ = 2-({3-[(2-hydroxy-benzylidene)-amino]-propylimino}-methyl)-phenol and DMF = N,N-dimethylformamide, have been synthesized starting with the precursor complex [NiL2]·2H2O, nickel(II) perchlorate and sodium nitrite and characterized structurally and magnetically. The structural analyses reveal that in all the complexes, NiII ions possess a distorted octahedral geometry. Complex 1 is a dinuclear di-m2-phenoxo bridged species in which nitrite ion acts as chelating co-ligand. Complexes 2a and 2b also consist of dinuclear entities, but in these two compounds a cis-(m-nitrito-1kO:2kN) bridge is present in addition to the di-m2-phenoxo bridge. The molecular structures of 2a and 2b are equivalent; they differ only in that 2a contains an additional solvated DMF molecule. Complex 3 is formed by ligand rearrangement and is a one-dimensional polymer in which double phenoxo as well as m-nitrito-1kO:2kN bridged trinuclear units are linked through a very rare m3-nitrito-1kO:2kN:3kO¢ bridge. Analysis of variable-temperature magnetic susceptibility data indicates that there is a global weak antiferromagnetic interaction between the nickel(II) ions in four complexes, with exchange parameters J of -5.26, -11.45, -10.66 and -5.99 cm-1 for 1, 2a, 2b and 3, respectively

Standardized test to evaluate numerical weather prediction algorithms

In order to assist in comparing the computational techniques used in different models, the authors propose a standardized set of one-dimensional numerical experiments that could be completed for each model. The results of these experiments, with a simplified form of the computational representation for advection, diffusion, pressure gradient term, Coriolis term, and filter used in the models, should be reported in the peer-reviewed literature. Specific recommendations are described in this paper.

Anion-directed template synthesis and hydrolysis of mono-condensed Schiff base of 1,3-pentanediamine ando-hydroxyacetophenone in NiII and CuII Complexes

Bis(o-hydroxyacetophenone)nickel(II) dihydrate, on reaction with 1,3-pentanediamine, yields a bis-chelate complex [NiL2]·2H2O (1) of mono-condensed tridentate Schiff baseligand HL {2-[1-(3-aminopentylimino)ethyl]phenol}. The Schiff base has been freed from the complex by precipitating the NiII as a dimethylglyoximato complex. HL reacts smoothly with Ni(SCN)2·4H2O furnishing the complex [NiL(NCS)] (2) and with CuCl2·2H2O in the presence of NaN3 or NH4SCN producing [CuL(N3)]2 (3) or [CuL(NCS)] (4). On the other hand, upon reaction with Cu(ClO4)2·6H2O and Cu(NO3)2·3H2O, the Schiff base undergoes hydrolysis to yield ternary complexes [Cu(hap)(pn)(H2O)]ClO4 (5) and [Cu(hap)(pn)(H2O)]NO3 (6), respectively (Hhap = o-hydroxyacetophenone and pn = 1,3-pentanediamine). The ligand HL undergoes hydrolysis also on reaction with Ni(ClO4)2·6H2O or Ni(NO3)2·6H2O to yield [Ni(hap)2] (7). The structures of the complexes 2, 3, 5, 6, and 7 have been confirmed by single-crystal X-ray analysis. In complex 2, NiII possesses square-planar geometry, being coordinated by the tridentate mono-negative Schiff base, L and the isothiocyanate group. The coordination environment around CuII in complex 3 is very similar to that in complex 2 but here two units are joined together by end-on, axial-equatorial azide bridges to result in a dimer in which the geometry around CuII is square pyramidal. In both 5 and 6, the CuII atoms display the square-pyramidal environment; the equatorial sites being coordinated by the two amine groups of 1,3-pentanediamine and two oxygen atoms of o-hydroxyacetophenone. The axial site is coordinated by a water molecule. Complex 7 is a square-planar complex with the Ni atom bonded to four oxygen atoms from two hap moieties. The mononuclear units of 2 and dinuclear units of 3 are linked by strong hydrogen bonds to form a one-dimensional network. The mononuclear units of 5 and 6 are joined together to form a dimer by very strong hydrogen bonds through the coordinated water molecule. These dimers are further involved in hydrogen bonding with the respective counteranions to form 2-D net-like open frameworks.

Correlation between Fourier series expansion and Hückel orbital theory

The Fourier series can be used to describe periodic phenomena such as the one-dimensional crystal wave function. By the trigonometric treatements in Hückel theory it is shown that Hückel theory is a special case of Fourier series theory. Thus, the conjugated π system is in fact a periodic system. Therefore, it can be explained why such a simple theorem as Hückel theory can be so powerful in organic chemistry. Although it only considers the immediate neighboring interactions, it implicitly takes account of the periodicity in the complete picture where all the interactions are considered. Furthermore, the success of the trigonometric methods in Hückel theory is not accidental, as it based on the fact that Hückel theory is a specific example of the more general method of Fourier series expansion. It is also important for education purposes to expand a specific approach such as Hückel theory into a more general method such as Fourier series expansion.

Assessing levels of uncertainty in recent temperature time series

We examine to what degree we can expect to obtain accurate temperature trends for the last two decades near the surface and in the lower troposphere. We compare temperatures obtained from surface observations and radiosondes as well as satellite-based measurements from the Microwave Soundings Units (MSU), which have been adjusted for orbital decay and non-linear instrument-body effects, and reanalyses from the European Centre for Medium-Range Weather Forecasts (ERA) and the National Centre for Environmental Prediction (NCEP). In regions with abundant conventional data coverage, where the MSU has no major influence on the reanalysis, temperature anomalies obtained from microwave sounders, radiosondes and from both reanalyses agree reasonably. Where coverage is insufficient, in particular over the tropical oceans, large differences are found between the MSU and either reanalysis. These differences apparently relate to changes in the satellite data availability and to differing satellite retrieval methodologies, to which both reanalyses are quite sensitive over the oceans. For NCEP, this results from the use of raw radiances directly incorporated into the analysis, which make the reanalysis sensitive to changes in the underlying algorithms, e.g. those introduced in August 1992. For ERA, the bias-correction of the one-dimensional variational analysis may introduce an error when the satellite relative to which the correction is calculated is biased itself or when radiances change on a time scale longer than a couple of months, e.g. due to orbit decay. ERA inhomogeneities are apparent in April 1985, October/November 1986 and April 1989. These dates can be identified with the replacements of satellites. It is possible that a negative bias in the sea surface temperatures (SSTs) used in the reanalyses may have been introduced over the period of the satellite record. This could have resulted from a decrease in the number of ship measurements, a concomitant increase in the importance of satellite-derived SSTs, and a likely cold bias in the latter. Alternately, a warm bias in SSTs could have been caused by an increase in the percentage of buoy measurements (relative to deeper ship intake measurements) in the tropical Pacific. No indications for uncorrected inhomogeneities of land surface temperatures could be found. Near-surface temperatures have biases in the boundary layer in both reanalyses, presumably due to the incorrect treatment of snow cover. The increase of near-surface compared to lower tropospheric temperatures in the last two decades may be due to a combination of several factors, including high-latitude near-surface winter warming due to an enhanced NAO and upper-tropospheric cooling due to stratospheric ozone decrease.

Estimation of optimal gravity wave parameters for climate models using data assimilation

There is a current need to constrain the parameters of gravity wave drag (GWD) schemes in climate models using observational information instead of tuning them subjectively. In this work, an inverse technique is developed using data assimilation principles to estimate gravity wave parameters. Because mostGWDschemes assume instantaneous vertical propagation of gravity waves within a column, observations in a single column can be used to formulate a one-dimensional assimilation problem to estimate the unknown parameters. We define a cost function that measures the differences between the unresolved drag inferred from observations (referred to here as the ‘observed’ GWD) and the GWD calculated with a parametrisation scheme. The geometry of the cost function presents some difficulties, including multiple minima and ill-conditioning because of the non-independence of the gravity wave parameters. To overcome these difficulties we propose a genetic algorithm to minimize the cost function, which provides a robust parameter estimation over a broad range of prescribed ‘true’ parameters. When real experiments using an independent estimate of the ‘observed’ GWD are performed, physically unrealistic values of the parameters can result due to the non-independence of the parameters. However, by constraining one of the parameters to lie within a physically realistic range, this degeneracy is broken and the other parameters are also found to lie within physically realistic ranges. This argues for the essential physical self-consistency of the gravity wave scheme. A much better fit to the observed GWD at high latitudes is obtained when the parameters are allowed to vary with latitude. However, a close fit can be obtained either in the upper or the lower part of the profiles, but not in both at the same time. This result is a consequence of assuming an isotropic launch spectrum. The changes of sign in theGWDfound in the tropical lower stratosphere, which are associated with part of the quasi-biennial oscillation forcing, cannot be captured by the parametrisation with optimal parameters.

Constraints on wave drag parameterization schemes for simulating the quasi-biennial oscillation. Part I: gravity wave forcing

Parameterization schemes for the drag due to atmospheric gravity waves are discussed and compared in the context of a simple one-dimensional model of the quasi-biennial oscillation (QBO). A number of fundamental issues are examined in detail, with the goal of providing a better understanding of the mechanism by which gravity wave drag can produce an equatorial zonal wind oscillation. The gravity wave–driven QBOs are compared with those obtained from a parameterization of equatorial planetary waves. In all gravity wave cases, it is seen that the inclusion of vertical diffusion is crucial for the descent of the shear zones and the development of the QBO. An important difference between the schemes for the two types of waves is that in the case of equatorial planetary waves, vertical diffusion is needed only at the lowest levels, while for the gravity wave drag schemes it must be included at all levels. The question of whether there is downward propagation of influence in the simulated QBOs is addressed. In the gravity wave drag schemes, the evolution of the wind at a given level depends on the wind above, as well as on the wind below. This is in contrast to the parameterization for the equatorial planetary waves in which there is downward propagation of phase only. The stability of a zero-wind initial state is examined, and it is determined that a small perturbation to such a state will amplify with time to the extent that a zonal wind oscillation is permitted.

Constraints on wave drag parameterization schemes for simulating the quasi-biennial oscillation. Part II: combined effects of gravity waves and equatorial planetary waves

This study examines the effect of combining equatorial planetary wave drag and gravity wave drag in a one-dimensional zonal mean model of the quasi-biennial oscillation (QBO). Several different combinations of planetary wave and gravity wave drag schemes are considered in the investigations, with the aim being to assess which aspects of the different schemes affect the nature of the modeled QBO. Results show that it is possible to generate a realistic-looking QBO with various combinations of drag from the two types of waves, but there are some constraints on the wave input spectra and amplitudes. For example, if the phase speeds of the gravity waves in the input spectrum are large relative to those of the equatorial planetary waves, critical level absorption of the equatorial planetary waves may occur. The resulting mean-wind oscillation, in that case, is driven almost exclusively by the gravity wave drag, with only a small contribution from the planetary waves at low levels. With an appropriate choice of wave input parameters, it is possible to obtain a QBO with a realistic period and to which both types of waves contribute. This is the regime in which the terrestrial QBO appears to reside. There may also be constraints on the initial strength of the wind shear, and these are similar to the constraints that apply when gravity wave drag is used without any planetary wave drag. In recent years, it has been observed that, in order to simulate the QBO accurately, general circulation models require parameterized gravity wave drag, in addition to the drag from resolved planetary-scale waves, and that even if the planetary wave amplitudes are incorrect, the gravity wave drag can be adjusted to compensate. This study provides a basis for knowing that such a compensation is possible.

Motion planning of autonomous vehicles in a non-autonomous vehicle environment without speed lanes

Planning is one of the key problems for autonomous vehicles operating in road scenarios. Present planning algorithms operate with the assumption that traffic is organised in predefined speed lanes, which makes it impossible to allow autonomous vehicles in countries with unorganised traffic. Unorganised traffic is though capable of higher traffic bandwidths when constituting vehicles vary in their speed capabilities and sizes. Diverse vehicles in an unorganised exhibit unique driving behaviours which are analysed in this paper by a simulation study. The aim of the work reported here is to create a planning algorithm for mixed traffic consisting of both autonomous and non-autonomous vehicles without any inter-vehicle communication. The awareness (e.g. vision) of every vehicle is restricted to nearby vehicles only and a straight infinite road is assumed for decision making regarding navigation in the presence of multiple vehicles. Exhibited behaviours include obstacle avoidance, overtaking, giving way for vehicles to overtake from behind, vehicle following, adjusting the lateral lane position and so on. A conflict of plans is a major issue which will almost certainly arise in the absence of inter-vehicle communication. Hence each vehicle needs to continuously track other vehicles and rectify plans whenever a collision seems likely. Further it is observed here that driver aggression plays a vital role in overall traffic dynamics, hence this has also been factored in accordingly. This work is hence a step forward towards achieving autonomous vehicles in unorganised traffic, while similar effort would be required for planning problems such as intersections, mergers, diversions and other modules like localisation.