Comparison of different uncertainty techniques in urban stormwater quantity and quality modelling

Urban drainage models are important tools used by both practitioners and scientists in the field of stormwater management. These models are often conceptual and usually require calibration using local datasets. The quantification of the uncertainty associated with the models is a must, although it is rarely practiced. The International Working Group on Data and Models, which works under the IWA/IAHR Joint Committee on Urban Drainage, has been working on the development of a framework for defining and assessing uncertainties in the field of urban drainage modelling. A part of that work is the assessment and comparison of different techniques generally used in the uncertainty assessment of the parameters of water models. This paper compares a number of these techniques: the Generalized Likelihood Uncertainty Estimation (GLUE), the Shuffled Complex Evolution Metropolis algorithm (SCEM-UA), an approach based on a multi-objective auto-calibration (a multialgorithm, genetically adaptive multi-objective method, AMALGAM) and a Bayesian approach based on a simplified Markov Chain Monte Carlo method (implemented in the software MICA). To allow a meaningful comparison among the different uncertainty techniques, common criteria have been set for the likelihood formulation, defining the number of simulations, and the measure of uncertainty bounds. Moreover, all the uncertainty techniques were implemented for the same case study, in which the same stormwater quantity and quality model was used alongside the same dataset. The comparison results for a well-posed rainfall/runoff model showed that the four methods provide similar probability distributions of model parameters, and model prediction intervals. For ill-posed water quality model the differences between the results were much wider; and the paper provides the specific advantages and disadvantages of each method. In relation to computational efficiency (i.e. number of iterations required to generate the probability distribution of parameters), it was found that SCEM-UA and AMALGAM produce results quicker than GLUE in terms of required number of simulations. However, GLUE requires the lowest modelling skills and is easy to implement. All non-Bayesian methods have problems with the way they accept behavioural parameter sets, e.g. GLUE, SCEM-UA and AMALGAM have subjective acceptance thresholds, while MICA has usually problem with its hypothesis on normality of residuals. It is concluded that modellers should select the method which is most suitable for the system they are modelling (e.g. complexity of the model’s structure including the number of parameters), their skill/knowledge level, the available information, and the purpose of their study.     

Reductive electrochemical remediation of emerging and regulated disinfection byproducts

Long-term exposure to low concentrations of disinfection byproducts (DBPs) in drinking water has been associated with increased human-health risks of bladder cancer and adverse reproductive outcomes. In this study, we investigated electrochemical reduction utilizing a resin-impregnated graphite cathode for the degradation of 17 DBPs (i.e. halomethanes, haloacetonitriles, halopropanones, chloral hydrate and trichloronitromethane) at low μg L⁻¹ concentration levels. The reduction experiments were potentiostatically controlled at cathode potentials −700, −800 and −900 mV vs Standard Hydrogen Electrode (SHE) during 24 h. At the lowest potential applied (i.e. −900 mV vs SHE), the disappearance of DBPs from the solution after 24 h of reduction was >70%, except for chloroform (32%), 1,1-dichloropropanone (48%), and chloral hydrate (31%). Due to the participation of several removal mechanisms (e.g. electrochemical reduction, adsorption, volatilization and/or hydrolysis) it was not possible to distinguish the removal efficiencies of electrochemical reduction of individual compounds. Adsorption of the more hydrophilic DBPs (i.e. haloacetonitriles, chloral hydrate, and 1,1-dichloropropanone) onto the electrode seems to be affected by the cathode polarization, as the removals observed in the open circuit experiments were significantly higher than the ones obtained in electrochemical reduction under the same conditions. The overall efficiency of reduction was estimated based on the analyses of the released Cl⁻, Br⁻ and I⁻ ions. Nearly complete C-I bond cleavage was achieved at all three potentials applied, and from the theoretically predicted release of I⁻ ions, calculated based on the removed DBPs, 86 ± 9 to 92 ± 1% was measured in the catholyte solution at −700 to −900 mV vs SHE. Debromination efficiencies obtained were 74 ± 3, 79 ± 6 and 68 ± 4% at −700, −800 and −900 mV vs SHE, while for C-Cl bond cleavage the obtained values were 69 ± 1, 72 ± 1 and 76 ± 4%, respectively. Nevertheless, dechlorination efficiencies are to be considered as approximate, since an increase in Cl⁻ concentration was observed in the open circuit experiments due to the hydrolysis of some of the chlorine-containing DBPs. Although the Coulombic efficiencies for DPBs dehalogenation were only 1.9 ± 0.3 (−900 mV vs SHE) -4.1 ± 0.2% (−700 mV vs SHE), relatively low energy consumption of the process was observed, estimated at 72 ± 2 Wh m⁻³ at −900 mV vs SHE for the concentration range of DBPs in this study (i.e. 65.3-129.7 μg L⁻¹). The study demonstrated that reductive electrochemical treatment has the potential to be a modern remediation technology for the removal of low concentrations of halogenated DBPs in water.     

Multiview deblurring for 3-D images from light-sheet-based fluorescence microscopy

We propose an algorithm for 3-D multiview deblurring using spatially variant point spread functions (PSFs). The algorithm is applied to multiview reconstruction of volumetric microscopy images. It includes registration and estimation of the PSFs using irregularly placed point markers (beads). We formulate multiview deblurring as an energy minimization problem subject to L1-regularization. Optimization is based on the regularized Lucy-Richardson algorithm, which we extend to deal with our more general model. The model parameters are chosen in a profound way by optimizing them on a realistic training set. We quantitatively and qualitatively compare with existing methods and show that our method provides better signal-to-noise ratio and increases the resolution of the reconstructed images.     

Free radical fast photo-cured gate dielectric for top-gate polymer field effect transistors

We demonstrated top-gate organic field effect transistors (OFETs) made with free radical photo-cured polymer gate dielectrics and poly(3-hexylthiophene). We introduced a new approach of cross linking dielectric polymers in OFETs by using acrylate monomers cured with UV irradiation directly on the semiconductor. Three different blends were formulated: one self-initiating acrylate oligomer and two epoxy acrylate monomers mixed with 4-phenylbenzophenone as photo initiator and N-methyldiethanolamine as amine synergist. Thin films of these blends were cured in air within one minute. The curing process was monitored with FT-IR spectroscopy and the effect of a wetting agent was studied by measuring the CV characteristics of metal–insulator-semiconductor (MIS) structures made with these formulations. OFETs made with the demonstrated formulations showed high on/off ratios (10⁵–10⁶) and low sub-threshold slopes (0.44–1.42 V/dec).     

Merocyanine/C60 Planar Heterojunction Solar Cells: Effect of Dye Orientation on Exciton Dissociation and Solar Cell Performance

In this study the charge dissociation at the donor/acceptor heterointerface of thermally evaporated planar heterojunction merocyanine/C₆₀ organic solar cells is investigated. Deposition of the donor material on a heated substrate as well as post‐annealing of the complete devices at temperatures above the glass transition temperature of the donor material results in a twofold increase of the fill factor. An analytical model employing an electric‐field‐dependent exciton dissociation mechanism reveals that geminate recombination is limiting the performance of as‐deposited cells. Fourier‐transform infrared ellipsometry shows that, at temperatures above the glass transition temperature of the donor material, the orientation of the dye molecules in the donor films undergoes changes upon annealing. Based on this finding, the influence of the dye molecules’ orientations on the charge‐transfer state energies is calculated by quantum mechanical/molecular mechanics methods. The results of these detailed studies provide new insight into the exciton dissociation process in organic photovoltaic devices, and thus valuable guidelines for designing new donor materials.     

Exploring the Origin of the Temperature‐Dependent Behavior of PbS Nanocrystal Thin Films and Solar Cells

Temperature‐dependent studies of the electrical and optical properties of cross‐linked PbS nanocrystal (NC) solar cells can provide deeper insight into their working mechanisms. It is demonstrated that the overall effect of temperature on the device efficiency originates from the temperature dependence of the open‐circuit voltage and the short‐circuit current, while the fill factor remains approximately constant. Extensive modeling provides signs of band‐like transport in the inhomogeneously coupled NC active layer and shows that the charge transport is dominated by diffusion. Moreover, via low temperature absorption and photoluminescence (PL) measurements, it is shown that the optical properties of PbS thin films before and after benzenedithiol (BDT) treatment exhibit very distinct behavior. After BDT treatment, both the optical density (OD) and PL are shifted to lower energies, indicating the occurrence of electronic wave function overlap between adjacent NCs. Decrease of the temperature leads to additional red‐shift of the OD and PL spectra, which is explained by the well‐known temperature dependence of the PbS NCs' bandgap. Moreover, BDT treated PbS NCs show unusual properties, such as decrease of the PL signal and broadening of the spectra at low temperatures. These features can be attributed to the partial relaxation of the quantum confinement and the opening of new radiative and nonradiative pathways for recombination at lower temperatures due to the presence of trap states.