MEASUREMENT AND MODELING OF THE TOXICITY OF BINARY MIXTURES IN THE NEMATODE CAENORHABDITIS ELEGANS-A TEST OF INDEPENDENT ACTION

Ecological risk assessments must increasingly consider the effects of chemical mixtures on the environment as anthropogenic pollution continues to grow in complexity. Yet testing every possible mixture combination is impractical and unfeasible; thus, there is an urgent need for models that can accurately predict mixture toxicity from single-compound data. Currently, two models are frequently used to predict mixture toxicity from single-compound data: Concentration addition and independent action (IA). The accuracy of the predictions generated by these models is currently debated and needs to be resolved before their use in risk assessments can be fully justified. The present study addresses this issue by determining whether the IA model adequately described the toxicity of binary mixtures of five pesticides and other environmental contaminants (cadmium, chlorpyrifos, diuron, nickel, and prochloraz) each with dissimilar modes of action on the reproduction of the nematode Caenorhabditis elegans. In three out of 10 cases, the IA model failed to describe mixture toxicity adequately with significant or antagonism being observed. In a further three cases, there was an indication of synergy, antagonism, and effect-level-dependent deviations, respectively, but these were not statistically significant. The extent of the significant deviations that were found varied, but all were such that the predicted percentage effect seen on reproductive output would have been wrong by 18 to 35% (i.e., the effect concentration expected to cause a 50% effect led to an 85% effect). The presence of such a high number and variety of deviations has important implications for the use of existing mixture toxicity models for risk assessments, especially where all or part of the deviation is synergistic.

Measurement and prediction of the effect of students activities on airborne particulate concentration in a classroom.

Epidemiological studies have shown links between human exposure to indoor airborne particles and adverse health affects. Several recent studies have also reported that the classroom environment has an impact on students’ health and performance. In this study particle concentration in a university classroom is assessed experimentally for different occupancy periods. The mass concentrations of different particle size ranges (0.3 – 20 µm), and the three particulate matter fractions (PM10, PM2.5, and PM1) were measured simultaneously in a classroom with different occupancy periods including occupied and unoccupied periods in the University of Reading, UK, during the winter period of 2010. The results showed that students’ presence is a significant factor affecting particles concentration for the fractions above PM1 in the measured range of 0.3 to 20 µm. The resuspension of the three PM fractions was also determined in the study.

Forecast, measurement, and modeling of an unprecedented polar ozone filament event over Mauna Loa Observatory, Hawaii

In mid-March 2005 the northern lower stratospheric polar vortex experienced a severe stretching episode, bringing a large polar filament far south of Alaska toward Hawaii. This meridional intrusion of rare extent, coinciding with the polar vortex final warming and breakdown, was followed by a zonal stretching in the wake of the easterly propagating subtropical main flow. This caused polar air to remain over Hawaii for several days before diluting into the subtropics. After being successfully forecasted to pass over Hawaii by the high-resolution potential vorticity advection model Modèle Isentrope du transport Méso-échelle de l'Ozone Stratosphérique par Advection (MIMOSA), the filament was observed on isentropic surfaces between 415 K and 455 K (17–20 km) by the Jet Propulsion Laboratory stratospheric ozone lidar measurements at Mauna Loa Observatory, Hawaii, between 16 and 19 March 2005. It was materialized as a thin layer of enhanced ozone peaking at 1.6 ppmv in a region where the climatological values usually average 1.0 ppmv. These values were compared to those obtained by the three-dimensional Chemistry-Transport Model MIMOSA-CHIM. Agreement between lidar and model was excellent, particularly in the similar appearance of the ozone peak near 435 K (18.5 km) on 16 March, and the persistence of this layer at higher isentropic levels for the following three days. Passive ozone, also modeled by MIMOSA-CHIM, was at about 3–4 ppmv inside the filament while above Hawaii. A detailed history of the modeled chemistry inside the filament suggests that the air mass was still polar ozone–depleted when passing over Hawaii. The filament quickly separated from the main vortex after its Hawaiian overpass. It never reconnected and, in less than 10 days, dispersed entirely in the subtropics

The calculation of force constants and normal coordinates IV: XH4 and XH3 molecules

Normal coordinate calculations of XH4 and XH3 molecules are reviewed and discussed. It is shown that for most of these molecules the true values of the force constants in the most General Harmonic Force Field can be uniquely determined only by making use of vibration-rotation interaction constants. It is emphasized that without these extra data the GFF is not determined. The results are compared with various model force fields for these molecules.

The calculation of accurate normal coordinates I: general theory, and application to methane

The calculation of accurate and reliable vibrational potential functions and normal co-ordinates is discussed, for such simple polyatomic molecules as it may be possible. Such calculations should be corrected for the effects of anharmonicity and of resonance interactions between the vibrational states, and should be fitted to all the available information on all isotopic species: particularly the vibrational frequencies, Coriolis zeta constants and centrifugal distortion constants. The difficulties of making these corrections, and of making use of the observed data are reviewed. A programme for the Ferranti Mercury Computer is described by means of which harmonic vibration frequencies and normal co-ordinate vectors, zeta factors and centrifugal distortion constants can be calculated, from a given force field and from given G-matrix elements, etc. The programme has been used on up to 5 × 5 secular equations for which a single calculation and output of results takes approximately l min; it can readily be extended to larger determinants. The best methods of using such a programme and the possibility of reversing the direction of calculation are discussed. The methods are applied to calculating the best possible vibrational potential function for the methane molecule, making use of all the observed data.

The calculation of force constants and normal co-ordinates II: methyl fluoride

The mathematical difficulties which can arise in the force constant refinement procedure for calculating force constants and normal co-ordinates are described and discussed. The method has been applied to the methyl fluoride molecule, using an electronic computer. The best values of the twelve force constants in the most general harmonic potential field were obtained to fit twenty-two independently observed experimental data, these being the six vibration frequencies, three Coriolis zeta constants and two centrifugal stretching constants DJ and DJK, for both CH3F and CD3F. The calculations have been repeated both with and without anharmonicity corrections to the vibration frequencies. All the experimental data were weighted according to the reliability of the observations, and the corresponding standard errors and correlation coefficients of the force constants have been deduced. The final force constants are discussed briefly, and compared with previous treatments, particularly with a recent Urey-Bradley treatment for this molecule.

The calculation of force constants and normal coordinates III: constrained force fields for the methyl halides

A method is discussed for imposing any desired constraint on the force field obtained in a force constant refinement calculation. The application of this method to force constant refinement calculations for the methyl halide molecules is reported. All available data on the vibration frequencies, Coriolis interaction constants and centrifugal stretching constants of CH3X and CD3X molecules were used in the refinements, but despite this apparent abundance of data it was found that constraints were necessary in order to obtain a unique solution to the force field. The results of unconstrained calculations, and of three different constrained calculations, are reported in this paper. The constrained models reported are a Urey—Bradley force field, a modified valence force field, and a constraint based on orbital-following bond-hybridization arguments developed in the following paper. The results are discussed, and compared with previous results for these molecules. The third of the above models is found to reproduce the observed data better than either of the first two, and additional reasons are given for preferring this solution to the force field for the methyl halide molecules.

The calculation of force constants and normal co-ordinates--VII Normal co-ordinates in the E species of allene

Force constant and normal co-ordinate calculations are reported for the E species vibrations of the allene molecule. Data on the fundamental vibration frequencies of allene-h4, allene-d4 and allene-1.1-d2 and on the five experimentally determined Coriolis zeta constants of C3H4 and C3D4, were used in a force constant refinement procedure. Allowing for product and sum rules this gives 21 independent data which were used to refine to the most general harmonic force field (10 parameters) with one constraint (in the absence of any constraints the refinement was not satisfactory). The results have been used to calculate the complete ζz Coriolis interaction matrix for the allene-1.1-d2 molecule, and hence to calculate the expected rotational structure of the perpendicular bending vibrations of this molecule; the good agreement obtained with the observed spectra is a check on our results.

Parcel theory in three dimensions and the calculation of SCAPE

Slantwise convective available potential energy (SCAPE) is a measure of the degree to which the atmosphere is unstable to conditional symmetric instability (CSI). It has, until now, been defined by parcel theory in which the atmosphere is assumed to be nonevolving and balanced, that is, two-dimensional. When applying this two-dimensional theory to three-dimensional evolving flows, these assumptions can be interpreted as an implicit assumption that a timescale separation exists between a relatively rapid timescale for slantwise ascent and a slower timescale for the development of the system. An approximate extension of parcel theory to three dimensions is derived and it is shown that calculations of SCAPE based on the assumption of relatively rapid slantwise ascent can be qualitatively in error. For a case study example of a developing extratropical cyclone, SCAPE calculated along trajectories determined without assuming the existence of the timescale separation show large SCAPE values for parcels ascending from the warm sector and along the warm front. These parcels ascend into the cloud head within which there is some evidence consistent with the release of CSI from observational and model cross sections. This region of high SCAPE was not found for calculations along the relatively rapidly ascending trajectories determined by assuming the existence of the timescale separation.