Surface volatilization modeling of (semi-)volatile hydrophobic organic compounds: The role of reference compounds.

Volatilization of hazardous hydrophobic organic compounds is often observed in many water, wastewater and soil treatment (bio)processes. Several models have been developed to quantify and predict gas-liquid pollutant transfer, being the proportionality coefficient model (PCM) one of the most commonly used, particularly in wastewater treatment. The PCM is based on the use of oxygen as a reference compound, which has a low resistance to the transfer in the gas phase. However, this resistance might be important for (semi-)volatile organic compounds - or (semi-)VOCs, which may render the use of the PCM model inaccurate. This study proposes an experimental methodology and a modeling approach for the use of the two-reference compound model (2RCM) that considers both the liquid-side and the gas-side resistances, by using water and oxygen as references. Results showed that the 2RCM predicts more accurately the overall mass transfer coefficients than the PCM for a VOC and two semi-VOCs tested in this study. In addition, the 2RCM was found to be a more robust method to estimate mass transfer coefficient of any compound and its use can be extrapolated to all substances. Finally, the relevance and limitations of both models was established.

Modelling gas-liquid mass transfer in wastewater treatment: when current knowledge needs to encounter engineering practice and vice versa.

Gas-liquid mass transfer in wastewater treatment processes has received considerable attention over the last decades from both academia and industry. Indeed, improvements in modelling gas-liquid mass transfer can bring huge benefits in terms of reaction rates, plant energy expenditure, acid-base equilibria and greenhouse gas emissions. Despite these efforts, there is still no universally valid correlation between the design and operating parameters of a wastewater treatment plant and the gas-liquid mass transfer coefficients. That is why the current practice for oxygen mass transfer modelling is to apply overly simplified models, which come with multiple assumptions that are not valid for most applications. To deal with these complexities, correction factors were introduced over time. The most uncertain of them is the α-factor. To build fundamental gas-liquid mass transfer knowledge more advanced modelling paradigms have been applied more recently. Yet these come with a high level of complexity making them impractical for rapid process design and optimisation in an industrial setting. However, the knowledge gained from these more advanced models can help in improving the way the α-factor and thus gas-liquid mass transfer coefficient should be applied. That is why the presented work aims at clarifying the current state-of-the-art in gas-liquid mass transfer modelling of oxygen and other gases, but also to direct academic research efforts towards the needs of the industrial practitioners.

Considering the plug-flow behavior of the gas phase in nitrifying BAF models significantly improves the prediction of N2O emissions.

Nitrifying biologically active filters (BAFs) have been found to be high emitters of nitrous oxide (N2O), a powerful greenhouse gas contributing to ozone layer depletion. While recent models have greatly improved our understanding of the triggers of N2O emissions from suspended-growth processes, less is known about N2O emissions from full-scale biofilm processes. Tertiary nitrifying BAFs have been modeled at some occasions but considering strong simplifications on the description of gas-liquid exchanges which are not appropriate for N2O prediction. In this work, a tertiary nitrifying BAF model including the main N2O biological pathways was developed and confronted to full-scale data from Seine Aval, the largest wastewater resource recovery facility in Europe. A mass balance on the gaseous compounds was included in order to correctly describe the N2O gas-liquid partition, thus N2O emissions. Preliminary modifications of the model structure were made to include the gas phase as a compartment of the model, which significantly affected the prediction of nitrification. In particular, considering gas hold-up influenced the prediction of the hydraulic retention time, thus nitrification performances: a 3.5% gas fraction reduced ammonium removal by 13%, as the liquid volume, small in such systems, is highly sensitive to the gas presence. Finally, the value of the volumetric oxygen transfer coefficient was adjusted to successfully predict both nitrification and N2O emissions.

Towards advanced aeration modelling: from blower to bubbles to bulk.

Aeration is an essential component of aerobic biological wastewater treatment and is the largest energy consumer at most water resource recovery facilities. Most modelling studies neglect the inherent complexity of the aeration systems used. Typically, the blowers, air piping, and diffusers are not modelled in detail, completely mixed reactors in a series are used to represent plug-flow reactors, and empirical correlations are used to describe the impact of operating conditions on bubble formation and transport, and oxygen transfer from the bubbles to the bulk liquid. However, the mechanisms involved are very complex in nature and require significant research efforts. This contribution highlights why and where there is a need for more detail in the different aspects of the aeration system and compiles recent efforts to develop physical models of the entire aeration system (blower, valves, air piping and diffusers), as well as adding rigour to the oxygen transfer efficiency modelling (impact of viscosity, bubble size distribution, shear and hydrodynamics). As a result of these model extensions, more realistic predictions of dissolved oxygen profiles and energy consumption have been achieved. Finally, the current needs for further model development are highlighted.

N2O emissions from full-scale nitrifying biofilters.

A full-scale nitrifying biofilter was continuously monitored during two measurement periods (September 2014; February 2015) during which both gaseous and liquid N2O fluxes were monitored on-line. The results showed diurnal and seasonal variations of N2O emissions. A statistical model was run to determine the main operational parameters governing N2O emissions. Modification of the distribution between the gas phase and the liquid phase was observed related to the effects of temperature and aeration flow on the volumetric mass transfer coefficient (kLa). With similar nitrification performance values, the N2O emission factor was twice as high during the winter campaign. The increase in N2O emissions in winter was correlated to higher effluent nitrite concentrations and suspected increased biofilm thickness.

Full-scale post denitrifying biofilters: sinks of dissolved N2O?

In this study, nitrous oxide (N2O) emissions from a full-scale denitrifying biofilter plant were continuously monitored over two periods (summer campaign in September 2014 and winter campaign in February 2015). Results of the summer campaign showed that the major part (>99%) of N2O flux was found in the liquid phase and was discharged with the effluent. N2O emissions were highly variable and represented in average 1.28±1.99% and 0.22±0.31% of the nitrate uptake rate during summer and winter campaigns, respectively. Denitrification was able to consume a large amount of dissolved N2O coming from the upstream nitrification stage. In the absence of methanol injection failure and with an influent BOD/NO3-N ratio higher than 3, average reduction of N2O was estimated to be of 93%. The control of exogenous carbon dosage is essential to minimize N2O production from denitrifying biofilters, in correlation to NO2-N concentrations in the filter.