Experimental and Theoretical Studies of the Environmental Sensitivity of the Absorption Spectra and Photochemistry of Nitenpyram and Analogs

Neonicotinoid (NN) pesticides have widespread use, largely replacing other pesticides such as the carbamates. Hence, there is a need to understand their environmental fates at a molecular level in various media, especially water. We report here the studies of a nitroenamine NN, nitenpyram (NPM), in aqueous solution where the absorption cross sections in the actinic region above 290 nm are observed to dramatically decrease compared to those in nonaqueous solvents. Quantum chemical calculations show that addition of a proton to the tertiary amine nitrogen in NPM breaks the conjugation in the chromophore, shifting the absorption to shorter wavelengths, consistent with experiment. However, surprisingly, adding a proton to the secondary amine nitrogen leads to its immediate transfer to the NO2 group, preserving the conjugation. This explains why the UV absorption of ranitidine (RAN), which has a similar chromophore but only secondary amine nitrogens, does not show a similar large blue shift in water. Photolysis quantum yields in aqueous NPM solutions were measured to be φ = 0.18 ± 0.07 at 254 nm, (9.4 ± 1.6) × 10-2 with broadband radiation centered at 313 nm and (5.2 ± 1.1) × 10-2 for broadband radiation centered at 350 nm (errors are 2σ). The major products in aqueous solutions are an imine that was also formed in the photolysis of the solid and a carboxylic acid derivative that is unique to the photolysis in water. Combining the larger quantum yields in water with the reduced absorption cross sections results in a calculated lifetime of NPM of only 5 min at a solar zenith angle of 35°, typical of 40°N latitude on April 1. The products do not absorb in the actinic region and hence will be long-lived with respect to photolysis

Model-based assessment of chromate reduction and nitrate effect in a methane-based membrane biofilm reactor

© 2019 Zhejiang University Chromate contamination can pose a high risk to both the environment and public health. Previous studies have shown that CH4-based membrane biofilm reactor (MBfR) is a promising method for chromate removal. In this study, we developed a multispecies biofilm model to study chromate reduction and its interaction with nitrate reduction in a CH4-based MBfR. The model-simulated results were consistent with the experimental data reported in the literature. The model showed that the presence of nitrate in the influent promoted the growth of heterotrophs, while suppressing methanotrophs and chromate reducers. Moreover, it indicated that a biofilm thickness of 150 μm and an influent dissolved oxygen concentration of 0.5 mg O2/L could improve the reactor performance by increasing the chromate removal efficiency under the simulated conditions

Nitrous Oxide Production in Co-Versus Counter-Diffusion Nitrifying Biofilms

For the application of biofilm processes, a better understanding of nitrous oxide (N 2 O) formation within the biofilm is essential for design and operation of biofilm reactors with minimized N 2 O emissions. In this work, a previously established N 2 O model incorporating both ammonia oxidizing bacteria (AOB) denitrification and hydroxylamine (NH 2 OH) oxidation pathways is applied in two structurally different biofilm systems to assess the effects of co-and counter-diffusion on N 2 O production. It is demonstrated that the diffusion of NH 2 OH and oxygen within both types of biofilms would form an anoxic layer with the presence of NH 2 OH and nitrite (), which would result in a high N 2 O production via AOB denitrification pathway. As a result, AOB denitrification pathway is dominant over NH 2 OH oxidation pathway within the co-and counter-diffusion biofilms. In comparison, the co-diffusion biofilm may generate substantially higher N 2 O than the counter-diffusion biofilm due to the higher accumulation of NH 2 OH in co-diffusion biofilm, especially under the condition of high-strength ammonium influent (500 mg N/L), thick biofilm depth (300 μm) and moderate oxygen loading (∼1-∼4 m 3 /d). The effect of co-and counter-diffusion on N 2 O production from the AOB biofilm is minimal when treating low-strength nitrogenous wastewater

Model-Based Feasibility Assessment of Membrane Biofilm Reactor to Achieve Simultaneous Ammonium, Dissolved Methane, and Sulfide Removal from Anaerobic Digestion Liquor

In this study, the membrane biofilm reactor (MBfR) is proposed to achieve simultaneous removal of ammonium, dissolved methane, and sulfide from main-stream and side-stream anaerobic digestion liquors. To avoid dissolved methane stripping, oxygen is introduced through gas-permeable membranes, which also from the substratum for the growth of a biofilm likely comprising ammonium oxidizing bacteria (AOB), anaerobic ammonium oxidation (Anammox) bacteria, denitrifying anaerobic methane oxidation (DAMO) microorganisms, aerobic methane oxidizing bacteria (MOB), and sulfur oxidizing bacteria (SOB). A mathematical model is developed and applied to assess the feasibility of such a system and the associated microbial community structure under different operational conditions. The simulation studies demonstrate the feasibility of achieving high-level (>97.0%), simultaneous removal of ammonium, dissolved methane, and sulfide in the MBfRs from both main-stream and side-stream anaerobic digestion liquors through adjusting the influent surface loading (or hydraulic retention time (HRT)) and the oxygen surface loading. The optimal HRT was found to be inversely proportional to the corresponding oxygen surface loading. Under the optimal operational conditions, AOB, DAMO bacteria, MOB, and SOB dominate the biofilm of the main-stream MBfR, while AOB, Anammox bacteria, DAMO bacteria, and SOB coexist in the side-stream MBfR to remove ammonium, dissolved methane, and sulfide simultaneously

Nitrous oxide production in a granule-based partial nitritation reactor: A model-based evaluation

Sustainable wastewater treatment has been attracting increasing attentions over the past decades. However, the production of nitrous oxide (N2O), a potent GHG, from the energy-efficient granule-based autotrophic nitrogen removal is largely unknown. This study applied a previously established N2O model, which incorporated two N2O production pathways by ammonia-oxidizing bacteria (AOB) (AOB denitrification and the hydroxylamine (NH 2 OH) oxidation). The two-pathway model was used to describe N2O production from a granule-based partial nitritation (PN) reactor and provide insights into the N2O distribution inside granules. The model was evaluated by comparing simulation results with N2O monitoring profiles as well as isotopic measurement data from the PN reactor. The model demonstrated its good predictive ability against N2O dynamics and provided useful information about the shift of N2O production pathways inside granules for the first time. The simulation results indicated that the increase of oxygen concentration and granule size would significantly enhance N2O production. The results further revealed a linear relationship between N2O production and ammonia oxidation rate (AOR) (R2 = 0.99) under the conditions of varying oxygen levels and granule diameters, suggesting that bulk oxygen and granule size may exert an indirect effect on N2O production by causing a change in AOR

Modeling aerobic biotransformation of vinyl chloride by vinyl chloride-assimilating bacteria, methanotrophs and ethenotrophs

© 2017 Elsevier B.V. Recent studies have investigated the potential of enhanced groundwater Vinyl Chloride (VC) remediation in the presence of methane and ethene through the interactions of VC-assimilating bacteria, methanotrophs and ethenotrophs. In this study, a mathematical model was developed to describe aerobic biotransformation of VC in the presence of methane and ethene for the first time. It examines the metabolism of VC by VC-assimilating bacteria as well as cometabolism of VC by both methanotrophs and ethenotrophs, using methane and ethene respectively, under aerobic conditions. The developed model was successfully calibrated and validated using experimental data from microcosms with different experimental conditions. The model satisfactorily describes VC, methane and ethene dynamics in all microcosms tested. Modeling results describe that methanotrophic cometabolism of ethene promotes ethenotrophic VC cometabolism, which significantly enhances aerobic VC degradation in the presence of methane and ethene. This model is expected to be a useful tool to support effective and efficient processes for groundwater VC remediation

A modeling approach to direct interspecies electron transfer process in anaerobic transformation of ethanol to methane

© 2016, Springer-Verlag Berlin Heidelberg. Recent studies have shown that direct interspecies electron transfer (DIET) plays an important part in contributing to methane production from anaerobic digestion. However, so far anaerobic digestion models that have been proposed only consider two pathways for methane production, namely, acetoclastic methanogenesis and hydrogenotrophic methanogenesis, via indirect interspecies hydrogen transfer, which lacks an effective way for incorporating DIET into this paradigm. In this work, a new mathematical model is specifically developed to describe DIET process in anaerobic digestion through introducing extracellular electron transfer as a new pathway for methane production, taking anaerobic transformation of ethanol to methane as an example. The developed model was able to successfully predict experimental data on methane dynamics under different experimental conditions, supporting the validity of the developed model. Modeling predictions clearly demonstrated that DIET plays an important role in contributing to overall methane production (up to 33 %) and conductive material (i.e., carbon cloth) addition would significantly promote DIET through increasing ethanol conversion rate and methane production rate. The model developed in this work will potentially enhance our current understanding on syntrophic metabolism via DIET

Microbial fuel cell for nutrient recovery and electricity generation from municipal wastewater under different ammonium concentrations

© 2019 Elsevier Ltd In the present study, a dual-compartment microbial fuel cell (MFC) was constructed and continuously operated under different influent concentrations of ammonium-nitrogen (5–40 mg/L). The impacts of ammonium on organics removal, energy output and nutrient recovery were investigated. Experimental results demonstrated that this MFC reactor achieved a CDO removal efficiency of greater than 85%. Moreover, excess ammonium concentration in the feed solution compromises the generation of electricity. Simultaneously, the recovery rate of phosphate achieved in the MFC was insignificantly influenced at the wider influent ammonium concentration. In contrast, a high concentration of ammonium may not be beneficial for its recovery

Monotonicity results and bounds for the inverse hyperbolic sine

In this note, we present monotonicity results of a function involving to the inverse hyperbolic sine. From these, we derive some inequalities for bounding the inverse hyperbolic sine.Comment: 3 page

A novel mechanistic model for nitrogen removal in algal-bacterial photo sequencing batch reactors

© 2018 Elsevier Ltd A comprehensive mathematical model was constructed to evaluate the complex substrate and microbial interaction in algal-bacterial photo sequencing batch reactors (PSBR). The kinetics of metabolite, growth and endogenous respiration of ammonia oxidizing bacteria, nitrite oxidizing bacteria and heterotrophic bacteria were coupled to those of microalgae and then embedded into widely-used activated sludge model series. The impact of light intensity was considered for microalgae growth, while the effect of inorganic carbon was considered for each microorganism. The integrated model framework was assessed using experimental data from algal-bacterial consortia performing sidestream nitritation/denitritation. The validity of the model was further evaluated based on dataset from PSBR performing mainstream nitrification. The developed model could satisfactorily capture the dynamics of microbial populations and substrates under different operational conditions (i.e. feeding, carbon dosing and illuminating mode, light intensity, influent ammonium concentration), which might serve as a powerful tool for optimizing the novel algal-bacterial nitrogen removal processes