Richard Spinney

Quantitative Structure–Activity Relationship (QSAR) for the Oxidation of Trace Organic Contaminants by Sulfate Radical

The sulfate radical anion (SO4•–) based oxidation of trace organic contaminants (TrOCs) has recently received great attention due to its high reactivity and low selectivity. In this study, a meta-analysis was conducted to better understand the role of functional groups on the reactivity between SO4•– and TrOCs. The results indicate that compounds in which electron transfer and addition channels dominate tend to exhibit a faster second-order rate constants (kSO4•–) than that of H–atom abstraction, corroborating the SO4•– reactivity and mechanisms observed in the individual studies. Then, a quantitative structure activity relationship (QSAR) model was developed using a sequential approach with constitutional, geometrical, electrostatic, and quantum chemical descriptors. Two descriptors, ELUMO and EHOMO energy gap (ELUMO–EHOMO) and the ratio of oxygen atoms to carbon atoms (#O:C), were found to mechanistically and statistically affect kSO4•– to a great extent with the standardized QSAR model: ln kSO4•– = 26.8–3.97 × #O:C – 0.746 × (ELUMO–EHOMO). In addition, the correlation analysis indicates that there is no dominant reaction channel for SO4•– reactions with various structurally diverse compounds. Our QSAR model provides a robust predictive tool for estimating emerging micropollutants removal using SO4•– during wastewater treatment processes.

Kinetics and Mechanism of the Oxidation of Cyclic Methylsiloxanes by Hydroxyl Radical in the Gas Phase: An Experimental and Theoretical Study

The ubiquitous presence of cyclic volatile methylsiloxanes (cVMS) in the global atmosphere has recently raised environmental concern. In order to assess the persistence and long-range transport potential of cVMS, their second-order rate constants (k) for reactions with hydroxyl radical ((•)OH) in the gas phase are needed. We experimentally and theoretically investigated the kinetics and mechanism of (•)OH oxidation of a series of cVMS, hexamethylcyclotrisiloxane (D3), octamethycyclotetrasiloxane (D4), and decamethycyclopentasiloxane (D5). Experimentally, we measured k values for D3, D4, and D5 with (•)OH in a gas-phase reaction chamber. The Arrhenius activation energies for these reactions in the temperature range from 313 to 353 K were small (-2.92 to 0.79 kcal·mol(-1)), indicating a weak temperature dependence. We also calculated the thermodynamic and kinetic behaviors for reactions at the M06-2X/6-311++G**//M06-2X/6-31+G** level of theory over a wider temperature range of 238-358 K that encompasses temperatures in the troposphere. The calculated Arrhenius activation energies range from -2.71 to -1.64 kcal·mol(-1), also exhibiting weak temperature dependence. The measured k values were approximately an order of magnitude higher than the theoretical values but have the same trend with increasing size of the siloxane ring. The calculated energy barriers for H-atom abstraction at different positions were similar, which provides theoretical support for extrapolating k for other cyclic siloxanes from the number of abstractable hydrogens.

Comparison of the reactivity of ibuprofen with sulfate and hydroxyl radicals: An experimental and theoretical study

Hydroxyl radical (•OH) and sulfate radical anion (SO4•-) based advanced oxidation technologies (AOTs) are effective methods to treat trace organic contaminants (TrOCs) in engineered waters. Although both technologies result in the same overall removal of TrOCs, the mechanistic differences between these two radicals involved in the oxidation of TrOCs remain unclear. In this study, we experimentally examined the degradation kinetics of neutral ibuprofen (IBU), a representative TrOC, by •OH and SO4•- at pH3 in UV/H2O2 and UV/persulfate systems, respectively. The second-order rate constants (k) of IBU with •OH and SO4•- were determined to be 3.43±0.06×109 and 1.66±0.12×109M-1s-1, respectively. We also theoretically calculated the thermodynamic and kinetic behaviors for reactions of IBU with •OH and SO4•- using the density functional theory (DFT) M06-2X method with 6-311++G** basis set. The results revealed that H-atom abstraction is the most favorable pathway for both •OH and SO4•-, but due to the steric hindrance SO4•- exhibits significantly higher energy barriers than •OH. The theoretical calculations corroborate our experimental observation that SO4•- has a smaller k value than •OH in reacting with IBU. These comparative results are of fundamental and practical importance in understanding the electrophilic interactions between radicals and IBU molecules, and to help select preferred radical oxidation processes for optimal TrOCs removal in engineered waters.

UV direct photolysis of sulfamethoxazole and ibuprofen: An experimental and modelling study

Photodegradation characteristics of pharmaceuticals and personal care products (PPCPs) during UV irradiation are of practical and scientific importance in selecting operational parameters during water treatment processes. In this study, the molar extinction coefficient (ε), quantum yield (φ), and degradation kinetics of neutral/anionic forms of sulfamethoxazole (SMX) and ibuprofen (IBU) were compared by varying solution pH. The degradation kinetics of the target compounds were observed to reversely correlate to the energy gap between highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) values of the target compounds. Then, a kinetic model for predicting the direct photolytic rates at different solution pH was established based on ε and φ of neutral/anionic species. The root mean squared errors for the modeled values suggest that the model exhibits good predictive power. Finally, in order to evaluate the electrical energy consumption during the UV direct photolysis process, the electrical energy per order (EE/O) was assessed. The experimental and modelling results are important to elucidate the mechanism of degradation of target PPCPs under UV irradiation and allow for the selection of optimal conditions in water treatment processes.

Chemical structure-based predictive model for the oxidation of trace organic contaminants by sulfate radical

Second-order rate constants [Formula: see text] for the reaction of sulfate radical anion (SO4•-) with trace organic contaminants (TrOCs) are of scientific and practical importance for assessing their environmental fate and removal efficiency in water treatment systems. Here, we developed a chemical structure-based model for predicting [Formula: see text] using 32 molecular fragment descriptors, as this type of model provides a quick estimate at low computational cost. The model was constructed using the multiple linear regression (MLR) and artificial neural network (ANN) methods. The MLR method yielded adequate fit for the training set (Rtraining2=0.88,n=75) and reasonable predictability for the validation set (Rvalidation2=0.62,n=38). In contrast, the ANN method produced a more statistical robustness but rather poor predictability (Rtraining2=0.99andRvalidation2=0.42). The reaction mechanisms of SO4•- reactivity with TrOCs were elucidated. Our result shows that the coefficients of functional groups reflect their electron donating/withdrawing characters. For example, electron donating groups typically exhibit positive coefficients, indicating enhanced SO4•- reactivity. Electron withdrawing groups exhibit negative values, indicating reduced reactivity. With its quick and accurate features, we applied this structure-based model to 55 discrete TrOCs culled from the Contaminant Candidate List 4, and quantitatively compared their removal efficiency with SO4•- and OH in the presence of environmental matrices. This high-throughput model helps prioritize TrOCs that are persistent to SO4•- based oxidation technologies at the screening level, and provide diagnostics of SO4•- reaction mechanisms.

A novel model to predict gas–phase hydroxyl radical oxidation kinetics of polychlorinated compounds

In this study, a novel model based on aromatic meta-substituent grouping was presented to predict the second-order rate constants (k) for OH oxidation of PCBs in gas-phase. Since the oxidation kinetics are dependent on the chlorination degree and position, we hypothesized that it may be more accurate for k value prediction if we group PCB congeners based on substitution positions (i.e., ortho (o), meta (m), and para (p)). To test this hypothesis, we examined the correlation of polarizability (α), a quantum chemical based descriptor for k values, with an empirical Hammett constant (σ+) on each substitution position. Our result shows that α is highly linearly correlated to ∑σo,m,p+ based on aromatic meta-substituents leading to the grouping based predictive model. With the new model, the calculated k values exhibited an excellent agreement with experimental measurements, and greater predictive power than the quantum chemical based quantitative structure activity relationship (QSAR) model. Further, the relationship of α and ∑σo,m,p+ for PCDDs congeners, together with highest occupied molecular orbital (HOMO) distribution, were used to validate the aromatic meta-substituent grouping method. This newly developed model features a combination of good predictability of quantum chemical based QSAR model and simplicity of Hammett relationship, showing a great potential for fast and computational tractable prediction of k values for gas-phase OH oxidation of polychlorinated compounds.

Indoor Tracking to Understand Physical Activity and Sedentary Behaviour: Exploratory Study in UK Office Buildings

Little is known of the patterns of physical activity, standing and sitting by office workers. However, insight into these behaviours is of growing interest, notably in regard to public health priorities to reduce non-communicable disease risk factors associated with high levels of sitting time and low levels of physical activity. With the advent and increasing availability of indoor tracking systems it is now becoming possible to build detailed pictures of the usage of indoor spaces. This paper reports initial results of indoor tracking used in conjunction with the ActivPAL activity monitoring device. In this paper we give an overview of the usage of the tracking system and its installation and illustrate some of the resultant data. We also provide preliminary results that investigate the relationship between location, light physical activity and sitting in a small sample of office workers (n=33) from two separate office environments in order to demonstrate the relevance and explanatory power of the technique.

Entropy production in full phase space for continuous stochastic dynamics

Total entropy production and its three constituent components are described both as fluctuating trajectory-dependent quantities and as averaged contributions in the context of the continuous Markovian dynamics, described by stochastic differential equations with multiplicative noise, of systems with both odd and even coordinates with respect to time reversal, such as dynamics in full phase space. Two of these constituent quantities obey integral fluctuation theorems and are thus rigorously positive in the mean due to Jensens inequality. The third, however, is not and furthermore cannot be uniquely associated with irreversibility arising from relaxation, nor with the breakage of detailed balance brought about by nonequilibrium constraints. The properties of the various contributions to total entropy production are explored through the consideration of two examples: steady-state heat conduction due to a temperature gradient, and transitions between stationary states of drift diffusion on a ring, both in the context of the full phase space dynamics of a single Brownian particle.

Quantitative structure–activity relationships for reactivities of sulfate and hydroxyl radicals with aromatic contaminants through single–electron transfer pathway

Sulfate radical anion (SO4•-) and hydroxyl radical (OH) based advanced oxidation technologies has been extensively used for removal of aromatic contaminants (ACs) in waters. In this study, we investigated the Gibbs free energy (ΔGSET∘) of the single electron transfer (SET) reactions for 76 ACs with SO4•- and OH, respectively. The result reveals that SO4•- possesses greater propensity to react with ACs through the SET channel than OH. We hypothesized that the electron distribution within the molecule plays an essential role in determining the ΔGSET∘ and subsequent SET reactions. To test the hypothesis, a quantitative structure-activity relationship (QSAR) model was developed for predicting ΔGSET∘ using the highest occupied molecular orbital energies (EHOMO), a measure of electron distribution and donating ability. The standardized QSAR models are reported to be ΔG°SET=-0.97×EHOMO - 181 and ΔG°SET=-0.97×EHOMO - 164 for SO4•- and OH, respectively. The models were internally and externally validated to ensure robustness and predictability, and the application domain and limitations were discussed. The single-descriptor based models account for 95% of the variability for SO4•- and OH. These results provide the mechanistic insight into the SET reaction pathway of radical and non-radical bimolecular reactions, and have important applications for radical based oxidation technologies to remove target ACs in different waters.

Transfer entropy in continuous time, with applications to jump and neural spiking processes

Transfer entropy has been used to quantify the directed flow of information between source and target variables in many complex systems. While transfer entropy was originally formulated in discrete time, in this paper we provide a framework for considering transfer entropy in continuous time systems, based on Radon-Nikodym derivatives between measures of complete path realizations. To describe the information dynamics of individual path realizations, we introduce the pathwise transfer entropy, the expectation of which is the transfer entropy accumulated over a finite time interval. We demonstrate that this formalism permits an instantaneous transfer entropy rate. These properties are analogous to the behavior of physical quantities defined along paths such as work and heat. We use this approach to produce an explicit form for the transfer entropy for pure jump processes, and highlight the simplified form in the specific case of point processes (frequently used in neuroscience to model neural spike trains). Finally, we present two synthetic spiking neuron model examples to exhibit the pertinent features of our formalism, namely, that the information flow for point processes consists of discontinuous jump contributions (at spikes in the target) interrupting a continuously varying contribution (relating to waiting times between target spikes). Numerical schemes based on our formalism promise significant benefits over existing strategies based on discrete time formalisms.