Long-lived halocarbon trends and budgets from atmospheric chemistry modelling constrained with measurements in polar firn

The budgets of seven halogenated gases (CFC-11, CFC-12, CFC-113, CFC-114, CFC-115, CCl4 and SF6) are studied by comparing measurements in polar firn air from two Arctic and three Antarctic sites, and simulation results of two numerical models: a 2-D atmospheric chemistry model and a 1-D firn diffusion model. The first one is used to calculate atmospheric concentrations from emission trends based on industrial inventories; the calculated concentration trends are used by the second one to produce depth concentration profiles in the firn. The 2-D atmospheric model is validated in the boundary layer by comparison with atmospheric station measurements, and vertically for CFC-12 by comparison with balloon and FTIR measurements. Firn air measurements provide constraints on historical atmospheric concentrations over the last century. Age distributions in the firn are discussed using a Green function approach. Finally, our results are used as input to a radiative model in order to evaluate the radiative forcing of our target gases. Multi-species and multi-site firn air studies allow to better constrain atmospheric trends. The low concentrations of all studied gases at the bottom of the firn, and their consistency with our model results confirm that their natural sources are small. Our results indicate that the emissions, sinks and trends of CFC-11, CFC-12, CFC-113, CFC-115 and SF6 are well constrained, whereas it is not the case for CFC-114 and CCl4. Significant emission-dependent changes in the lifetimes of halocarbons destroyed in the stratosphere were obtained. Those result from the time needed for their transport from the surface where they are emitted to the stratosphere where they are destroyed. Efforts should be made to update and reduce the large uncertainties on CFC lifetimes.

Laboratory measurements of the water vapor continuum in the 1200–8000 cm−1 region between 293 K and 351 K

Laboratory Fourier transform spectroscopy of pure water vapor and water vapor mixed with air has been conducted between 1200 and 8000 cm−1 and at temperatures between 293 and 351 K with the purpose of detecting and characterizing the water vapor continuum. The spectral features of the continuum within the major water absorption bands are presented and compared where possible to those from previous experimental studies and to the commonly used MT_CKD and CKD models. It was observed that in the main, both models adequately capture the general spectral form of the continuum; however, there were a number of exceptions. Overall, there is no evidence to indicate that MT_CKD is an improvement upon the older CKD model in these spectral regions. There was generally good agreement between our results and those of other experimental investigators. The general mathematical forms of the self-continuum temperature dependence, given by both Roberts et al. (1976) and CKD/MT_CKD, fit well to the experimental continuum in these spectral regions. However, the range of temperatures over which we made measurements is not sufficient to discriminate between these two forms or to exclude the possibility of other forms of temperature dependence being more appropriate. At the same time, the actual parameters currently used in CKD/MT_CKD to describe the temperature dependence in many spectral regions cannot reproduce the observed strong spectral variation in the temperature dependence. It has not been possible to make definitive conclusions about the magnitude of the continuum absorption in the far wings of the absorption bands investigated here.

Gas-phase kinetics of chlorosilylene reactions II. ClSiH + C2H4: absolute rate measurements and quantum chemical and RRKM calculations for the prototype pi addition reaction

Time-resolved studies of chlorosilylene, ClSiH, generated by the 193 nm laser flash photolysis of 1-chloro-1-silacyclopent-3-ene, are carried out to obtain rate constants for its bimolecular reaction with ethene, C2H4, in the gas-phase. The reaction is studied over the pressure range 0.13-13.3 kPa (with added SF6) at five temperatures in the range 296-562 K. The second order rate constants, obtained by extrapolation to the high pressure limits at each temperature, fitted the Arrhenius equation: log(k(infinity)/cm(3) molecule(-1) s(-1))=(-10.55 +/- 0.10) + (3.86 +/- 0.70) kJ mol(-1)/RT ln10. The Arrhenius parameters correspond to a loose transition state and the rate constant at room temperature is 43% of that for SiH2 + C2H4, showing that the deactivating effect of Cl-for-H substitution in the silylene is not large. Quantum chemical calculations of the potential energy surface for this reaction at the G3MP2//B3LYP level show that, as well as 1-chlorosilirane, ethylchlorosilylene is a viable product. The calculations reveal how the added effect of the Cl atom on the divalent state stabilisation of ClSiH influences the course of this reaction. RRKM calculations of the reaction pressure dependence suggest that ethylchlorosilylene should be the main product. The results are compared and contrasted with those of SiH2 and SiCl2 with C2H4.

Evaluation of a Lagrangian box model using field measurements from EASE (Eastern Atlantic Summer Experiment) 1996

The Cambridge Tropospheric Trajectory model of Chemistry and Transport (CiTTyCAT), a Lagrangian chemistry model, has been evaluated using atmospheric chemical measurements collected during the East Atlantic Summer Experiment 1996 (EASE '96). This field campaign was part of the UK Natural Environment Research Council's (NERC) Atmospheric Chemistry Studies in the Oceanic Environment (ACSOE) programme, conducted at Mace Head, Republic of Ireland, during July and August 1996. The model includes a description of gas-phase tropospheric chemistry, and simple parameterisations for surface deposition, mixing from the free troposphere and emissions. The model generally compares well with the measurements and is used to study the production and loss of O3 under a variety of conditions. The mean difference between the hourly O3 concentrations calculated by the model and those measured is 0.6 ppbv with a standard deviation of 8.7 ppbv. Three specific air-flow regimes were identified during the campaign – westerly, anticyclonic (easterly) and south westerly. The westerly flow is typical of background conditions for Mace Head. However, on some occasions there was evidence of long-range transport of pollutants from North America. In periods of anticyclonic flow, air parcels had collected emissions of NOx and VOCs immediately before arriving at Mace Head, leading to O3 production. The level of calculated O3 depends critically on the precise details of the trajectory, and hence on the emissions into the air parcel. In several periods of south westerly flow, low concentrations of O3 were measured which were consistent with deposition and photochemical destruction inside the tropical marine boundary layer.

The use of trajectory cluster analysis to interpret trace gas measurements at Mace Head, Ireland

A first step in interpreting the wide variation in trace gas concentrations measured over time at a given site is to classify the data according to the prevailing weather conditions. In order to classify measurements made during two intensive field campaigns at Mace Head, on the west coast of Ireland, an objective method of assigning data to different weather types has been developed. Air-mass back trajectories calculated using winds from ECMWF analyses, arriving at the site in 1995–1997, were allocated to clusters based on a statistical analysis of the latitude, longitude and pressure of the trajectory at 12 h intervals over 5 days. The robustness of the analysis was assessed by using an ensemble of back trajectories calculated for four points around Mace Head. Separate analyses were made for each of the 3 years, and for four 3-month periods. The use of these clusters in classifying ground-based ozone measurements at Mace Head is described, including the need to exclude data which have been influenced by local perturbations to the regional flow pattern, for example, by sea breezes. Even with a limited data set, based on 2 months of intensive field measurements in 1996 and 1997, there are statistically significant differences in ozone concentrations in air from the different clusters. The limitations of this type of analysis for classification and interpretation of ground-based chemistry measurements are discussed.

Comparison and visualisation of high-resolution transport modelling with aircraft measurements

This article presents a case study of a comparison of an Eulerian chemical transport model (CTM) and Lagrangian chemical model with measurements taken by aircraft. High-resolution Eulerian integrations produce improved point-by-point comparisons between model results and measurements compared to low resolution. The Lagrangian model requires mixing to be introduced in order to model the measurements.

The spatial distribution of carbon dioxide in an environmental test chamber

The spatial distribution of CO2 level in a classroom carried out in previous field work research has demonstrated that there is some evidence of variations in CO2 concentration in a classroom space. Significant fluctuations in CO2 concentration were found at different sampling points depending on the ventilation strategies and environmental conditions prevailing in individual classrooms. However, how these variations are affected by the emitting sources and the room air movement remains unknown. Hence, it was concluded that detailed investigation of the CO2 distribution need to be performed on a smaller scale. As a result, it was decided to use an environmental chamber with various methods and rates of ventilation, for the same internal temperature and heat loads, to study the effect of ventilation strategy and air movement on the distribution of CO2 concentration in a room. The role of human exhalation and its interaction with the plume induced by the body's convective flow and room air movement due to different ventilation strategies were studied in a chamber at the University of Reading. These phenomena are considered to be important in understanding and predicting the flow patterns in a space and how these impact on the distribution of contaminants. This paper attempts to study the CO2 dispersion and distribution at the exhalation zone of two people sitting in a chamber as well as throughout the occupied zone of the chamber. The horizontal and vertical distributions of CO2 were sampled at locations with a probability that CO2 variation is considered high. Although the room size, source location, ventilation rate and location of air supply and extract devices all can have influence on the CO2 distribution, this article gives general guidelines on the optimum positioning of CO2 sensor in a room.

Thermal comfort assessment in a non-uniform thermal environment

This paper presents results for thermal comfort assessment in non-uniform thermal environments. Three types of displacement ventilation (DV) units that created stratified condition in an environmental test chamber have been selected to carry out the thermal comfort assessment: a flat diffuser (DV1), semi-circular diffuser (DV2), and floor swirl diffuser (DV3). The CBE (Center for the Built Environment at Berkeley) comfort model was implemented in this study to assess the occupant’s thermal comfort for the three DV types. The CBE model predicted the occupant’s mean skin as well as local skin temperatures very well when compared with measurements found in the literature, while it underestimated the occupant’s core temperature. The predicted occupant’s thermal sensation and thermal comfort for the case of (DV2) were the best. Therefore, the semi-circular diffuser (DV2) provided better thermal comfort for the occupant in comparison with the other two DV types.

Gas-phase kinetics of chlorosilylene reactions. I. ClSiH + Me3SiH: absolute rate measurements and theoretical calculations for prototype Si−H insertion reactions

Time-resolved studies of chlorosilylene, CISiH, generated by the 193 nm laser flash photolysis of 1-chloro-1-silacyclopent-3-ene, have been carried out to obtain rate constants for its bimolecular reaction with trimethylsilane, Me3SiH, in the gas phase. The reaction was studied at total pressures up to 100 torr (with and without added SF6) over the temperature range 297-407 K. The rate constants were found to be pressure independent and gave the following Arrhenius equation: log(k/cm(3) molecule(-1) s(-1)) = (-13.97 +/- 0.25) + (12.57 +/- 1.64) kJ mol(-1)/RT In 10. The Arrhenius parameters are consistent with a mechanism involving an intermediate complex, whose rearrangement is the rate-determining step. Quantum chemical calculations of the potential energy surface for this reaction and also the reactions of CISiH with SiH4 and the other methylsilanes support this conclusion. Comparisons of both experiment and theory with the analogous Si-H insertion processes of SiH2 and SiMe2 show that the main factor causing the lower reactivity of ClSiH is the secondary energy barrier. The calculations also show the existence of a novel intramolecular H-atom exchange process in the complex of ClSiH with MeSiH3.

Analysis of spectroscopic measurements of leaf water content at terahertz frequencies using linear transforms

We provide a unified framework for a range of linear transforms that can be used for the analysis of terahertz spectroscopic data, with particular emphasis on their application to the measurement of leaf water content. The use of linear transforms for filtering, regression, and classification is discussed. For illustration, a classification problem involving leaves at three stages of drought and a prediction problem involving simulated spectra are presented. Issues resulting from scaling the data set are discussed. Using Lagrange multipliers, we arrive at the transform that yields the maximum separation between the spectra and show that this optimal transform is equivalent to computing the Euclidean distance between the samples. The optimal linear transform is compared with the average for all the spectra as well as with the Karhunen–Loève transform to discriminate a wet leaf from a dry leaf. We show that taking several principal components into account is equivalent to defining new axes in which data are to be analyzed. The procedure shows that the coefficients of the Karhunen–Loève transform are well suited to the process of classification of spectra. This is in line with expectations, as these coefficients are built from the statistical properties of the data set analyzed.

Measurements of leaf water content using terahertz radiation

A novel technique for the noninvasive continuous measurement of leaf water content is presented. The technique is based on transmission measurements of terahertz radiation with a null-balance quasi-optical transmissometer operating at 94 GHz. A model for the propagation of terahertz radiation through leaves is presented. This, in conjunction with leaf thickness information determined separately, may be used to quantitatively relate transmittance measurements to leaf water content. Measurements using a dispersive Fourier transform spectrometer in the range of 100 GHz-500 GHz using Phormium tenax and Fatsia japonica leaves are also reported.

Precision of quasi-optical null-balanced bridge techniques for transmission and reflection coefficient measurements

The precision of quasioptical null-balanced bridge instruments for transmission and reflection coefficient measurements at millimeter and submillimeter wavelengths is analyzed. A Jones matrix analysis is used to describe the amount of power reaching the detector as a function of grid angle orientation, sample transmittance/reflectance and phase delay. An analysis is performed of the errors involved in determining the complex transmission and reflection coefficient after taking into account the quantization error in the grid angle and micrometer readings, the transmission or reflection coefficient of the sample, the noise equivalent power of the detector, the source power and the post-detection bandwidth. For a system fitted with a rotating grid with resolution of 0.017 rad and a micrometer quantization error of 1 μm, a 1 mW source, and a detector with a noise equivalent power 5×10−9 W Hz−1/2, the maximum errors at an amplitude transmission or reflection coefficient of 0.5 are below ±0.025.

Millimeter-wave measurements of the complex dielectric constant of an advanced thick film UV photoresist

The first measurement of the relative permittivity (εr) and loss tangent (tan δ) of EPON™ SU-8 advanced thick film ultraviolet photoresist is reported at frequencies between 75–110 GHz (W-band). The problems associated with such a measurement are discussed, an error analysis given, and values of εr=1.725±0.08 and tanδ =0.02±0.001 are determined.

Distributed water ingress and water potential measurements using fibre optics

We report on a distributed moisture detection scheme which uses a cable design based on waterswellable hydrogel polymers. The cable modulates the loss characteristic of light guided within a multi-mode optical fibre in response to relative water potentials in the surrounding environment. Interrogation of the cable using conventional optical time-domain reflectometry (OTDR) instruments allows water ingress points to be identified and located with a spatial resolution of 50 cm. The system has been tested in a simulated tendon duct grouting experiment as a means of mapping the extent of fill along the duct during the grouting process. Voided regions were detected and identified to within 50 cm. A series of salt solutions has been used to determine the sensor behaviour over a range of water potentials. These experiments predict that measurements of soil moisture content can be made over the range 0 to – 1500 kPa. Preliminary data on soil measurements have shown that the sensor can detect water pressure changes with a resolution of 45 kPa. Applications for the sensor include quality assurance of grouting procedures, verification of waterproofing barriers and soil moisture content determination (for load-bearing calculations).