Disinfection by products estimation in a water distribution network

Even though disinfection is necessary to ensure water safety for human consumption, some disinfectants produce disinfection by-products (DBPs) that may be dangerous for human health. Current European legislation obligates water distributors to limit some DBPs concentration to final consumers. Then, water companies must control these compounds and are obligated to periodically monitor their network. DBPs modeling can be very useful for estimating online DBPs concentration throughout the network, increasing DBPs control and knowledge, but avoiding DBPs analytics time and resources consumption [1]. Trihalomethanes (THM), the first DBPs discovered, have long been the most studied and modeled. Previous studies have mostly used linear relations between variables and THM concentration, but also computational modelling, mechanistic and data driven models [2, 3]. Even though, there are still challenges to beat: most studies use a small database and laboratory-scale for model building, forgetting the impact of network pipelines and season. In addition, significant variables for DBPs’ formation such as retention time are most of the time neglected due to its difficulty to measure. Finally, THMs are not the only DBPs generated from disinfection or even the most toxic: other DBPs must be studied, and their formation pathways along the network investigated. In this study, data from a full-scale distribution network was used: online sensors and sampling campaigns. To include hydraulic conditions as retention time, EPANET software and R programming are used to simulate the network. Different models, mechanistic and data driven, have been used to estimate the chlorine decay and DBP formation within the network. Results of the calibration and validation of these models and the conclusions obtained are presented.Peer ReviewedPostprint (published version

A review: biological technologies for nitrogen monoxide abatement

David Cubides is a fellow of Eurecat's “Vicente López” PhD grant program. This work was financially supported by the Catalan government through the funding grant ACCIÓ-Eurecat (Project PRIV 2020/21-AIRECAT). The authors acknowledge the Spanish Government, through project RTI 2018-099362-B-C21 MINECO/FEDER, EU, for the financial support provided to perform this research.Peer ReviewedPostprint (published version

La Tècnica FISH i el microscopi confocal aplicats a la determinació de fraccions de biomassa en un reactor aerobi nitrificant

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Mass transfer vectors for nitric oxide removal through biological treatments

The reduction of nitric oxide (NO) emissions to atmosphere has been recently addressed using biological technologies. However, NO removal through bioprocesses is quite challenging due to the low solubility of NO in water. Therefore, the abatement of NO emissions might be improved by adding a chelating agent or a mass transfer vector (MTV) to increase the solubility of this pollutant into the aqueous phase where the bioprocess takes place. This research seeks to assess the performance of different non-aqueous phase liquids (NAPs): n-hexadecane (HEX), diethyl sebacate (DSE), 1,1,1,3,5,5,5-heptamethyl-trisiloxane (HTX), 2,2,4,4,6,8,8-heptamethylnonane (HNO), and high temperature silicone oil (SO) in chemical absorption–biological reduction (CABR) integrated systems. The results showed that HNO and HTX had the maximum gas-liquid mass transfer capacity, being 0.32 mol NO/kmol NAP and 0.29 mol NO/kmol NAP, respectively. When an aqueous phase was added to the system, the mass transfer gas–liquid of NO was increased, with HTX reaching a removal efficiency of 82 ± 3% NO with water, and 88 ± 6% with a phosphate buffer solution. All NAPs were tested for short-term toxicity assessment and resulted neither toxic nor inhibitory for the biological activity (denitrification). DSE was found to be biodegradable, which could limit its applicability in biological processes for gas treatment. Finally, in the CABR system tests, it was shown that NO elimination improved in a short time (30 min) when the three mass transfer vectors (HEX, HTX, HNO) were added to enriched denitrifying bacteria.Open Access funding provided thanks to the CRUE-CSIC agreement with Springer Nature. David Cubides is a fellow of Eurecat’s “Vicente López” PhD grant program. This work was financially supported by the Catalan Government through the funding grant ACCIÓ-Eurecat (Project PRIV2020/21-AIRECAT). The authors acknowledge the Spanish Government, through the project RTI2018-099362-B-C21 MINECO/FEDER, EU, for the financial support provided to perform this research.Peer ReviewedPostprint (published version

Chlorine concentration modelling and supervision in water distribution systems

The quality of the drinking water distributed through the networks has become the main concern of most operators. This work focuses on one of the most important variables of the drinking water distribution networks (WDN) that use disinfection, chlorine. This powerful disinfectant must be dosed carefully in order to reduce disinfection byproducts (DBPs). The literature demonstrates researchers’ interest in modelling chlorine decay and using several different approaches. Nevertheless, the full-scale application of these models is far from being a reality in the supervision of water distribution networks. This paper combines the use of validated chlorine prediction models with an intensive study of a large amount of data and its influence on the model’s parameters. These parameters are estimated and validated using data coming from the Supervisory Control and Data Acquisition (SCADA) software, a full-scale water distribution system, and using off-line analytics. The result is a powerful methodology for calibrating a chlorine decay model on-line which coherently evolves over time along with the significant variables that influence it.Peer ReviewedPostprint (author's final draft

Operation, modeling and automatic control of complete and partial nitrification of highly concentrated ammonium wastewater

El tema d'estudi d'aquesta tesi és l'eliminació biològica de nitrogen d'aigües amb alta càrrega d'amoníac, més concretament, el procés de nitrificació (l'oxidació de l'amoni a nitrat). Aquesta reacció en dos passos, catalitzada per dos tipus de microorganismes (AOB i NOB), pot patir problemes d'inhibicions per amoníac i àcid nitrós. Això és especialment important quan es tracta aigua amb alta concentració d'amoni i per tant, es necessita un control del procés adequat. Tot i així, aquestes inhibicions es poden utilitzar per a aconseguir nitrificació parcial (l'oxidació de l'amoni a nitrit), la qual combinada amb el procés de desnitrificació, aporta beneficis importants pel què fa a la utilització dels recursos.En aquesta tesi es mostra el desenvolupament i calibratge d'un model matemàtic per a descriure la cinètica i l'estequiometria de la nitrificació considerant les inhibicions mencionades anteriorment i tenint en compte els dos tipus de bacteris nitrificants i també els bacteris heteròtrofs. Es varen dissenyar experiments específics per a l'optimització dels paràmetres del model i amb l'ajuda d'eines d'identificabilitat de paràmetres, aquests experiments es van analitzar i millorar. Les constants d'afinitat pel substrat i els coeficients d'inhibició per substrat es van determinar dues vegades utilitzant biomasses diferents i es van obtenir resultats diferents. Això indicà que aquests paràmetres són variables i depenen de l'aclimatació de la biomassa. Es va utilitzar la tècnica d'hibridació fluorescent in situ (FISH) per a la detecció i quantificació de les fraccions bacterianes. Per a la detecció de la fluorescència es van utilitzar un microscopi d'epifluorescència, un microscopi confocal i un citòmetre de flux. Els resultats obtinguts es van comparar entre ells i es van discutir els seus avantatges i inconvenients tenint en compte la precisió dels resultats, la velocitat de l'anàlisi i la disponibilitat de l'equip. La millor metodologia va resultar ser l'observació del FISH amb el microscopi confocal encara que la citometria de flux no es va poder investigar prou a fons. El model matemàtic desenvolupat i calibrat en aquesta tesi es va utilitzar per a l'optimització de la posada en marxa d'un sistema de nitrificació completa. Es van optimitzar dues estratègies de control que posteriorment es van implementar experimentalment partint d'un inòcul procedent dels llots d'una estació de tractament d'aigües residuals urbanes. El controlador dissenyat es basava en la mesura de la velocitat del consum d'oxigen (OUR) en l'últim reactor del sistema i actuava sobre la càrrega d'entrada. Els resultats obtinguts es van comparar amb els resultats d'una posada en marxa amb control manual i es va demostrar que el control automàtic permet disminuir el temps de posada en marxa i augmentar l'estabilitat del procés. Posteriorment, els resultats experimentals es van simular amb el model matemàtic obtenint un bon ajust. Finalment, el nou model es va utilitzar per a fer prediccions del comportament del sistema a curt i llarg termini. L'enriquiment de la biomassa en microorganismes nitrificants es va comprovar mitjançant el FISH i la microscòpia confocal. La biomassa que es va obtenir després de la última posada en marxa del sistema es va utilitzar per a aconseguir la nitrificació parcial treballant a 25 ºC, 1.1 mg O2 L-1, pH de 8.3 i amb un set point d'OUR apropiat en el control automàtic. La nitrificació parcial es va mantenir de forma estable durant uns 120 dies amb una càrrega mitjana de 0.5 g N g-1 SSV d-1. L'anàlisi microbiològic amb FISH va demostrar que la població de NOB havia estat eliminada del sistema. Posteriorment, el sistema de control es va millorar amb l'adició de dues regles de control expert que van permetre l'operació estable del sistema davant d'importants pertorbacions externes.Biological nitrogen removal of high-strength ammonium wastewater was studied in this thesis, particularly, the nitrification process (the oxidation of ammonium to nitrate). This two-step reaction, catalyzed by two kinds of bacteria (AOB and NOB), can suffer serious inhibition problems due to ammonia and nitrous acid when dealing with highly concentrated ammonium wastewater and therefore it requires adequate process control. However, these inhibitions can be used to achieve partial nitrification (the oxidation of ammonium to nitrite), which coupled to a denitrifying process leads to significant benefits in terms of use of resources.A mathematical model describing the kinetics and the stoichiometry of the nitrification process was developed and calibrated. It considered the aforementioned inhibitions and took into account both kinds of nitrifying bacteria and also heterotrophic bacteria. Specific experiments were designed for parameter estimation and parameter identifiability tools were used to analyze and improve them. Optimal experimental designs were used to calibrate most of the model parameters and the obtained values were compared with values found in the literature. Affinity constants for substrate and substrate inhibition coefficients were estimated twice using different sludges and, as a result, different values were found indicating that they change depending on the biomass acclimation. This model was coupled to the hydraulic model of the experimental system (pilot plant) and was implemented in Matlab ®. Fluorescence in situ hybridization (FISH) was used for bacterial fractions detection and quantification. Several equipments were used for fluorescence detection: an epifluorescence microscope, a confocal microscope and a flow cytometer. Biomass fractions were determined with each of the equipment and also with simulations. Obtained results were compared and the advantages and disadvantages of the tested methodologies were discussed considering the accuracy of the results, the speed of the analysis and the availability of the equipment. FISH combined with confocal microscopy turned out to be the best technique for nitrifying biomass quantification although flow cytometry could not be extensively investigated.The start-up of a complete nitrification system was optimized by means of mathematical simulation using the previously developed and calibrated method. Two automatic control strategies were optimized and implemented in the experimental system by using sludge from a municipal wastewater treatment plant as inoculum. The controller was based on the measurement of the oxygen uptake rate (OUR) in the last reactor of the system and actuated over the nitrogen loading rate. Results were compared with a start-up performed with manual control and it was demonstrated that automatic control decreased the length of the start-up and increased its stability. Then, experimental results were simulated with the nitrification model. Model predictions agreed well with experimental data. The final model was useful for both long- and short-term prediction. The sludge enrichment in nitrifying bacteria was checked with FISH and confocal microcopy.The nitrifying sludge obtained after the last start-up contained both AOB an NOB and was used to achieve partial nitrification. Some environmental conditions and the automatic control strategy were changed in order to inhibit NOB and wash them out of the system. Partial nitrification with an effluent devoid of nitrate was achieved at 25 ºC, 1.1 mg O2 L-1 and pH of 8.3 using the appropriate OUR set point for the automatic controller. Partial nitrification was run for 120 days with an averaged nitrogen loading rate of 0.5 g N g-1 VSS d-1. FISH analysis demonstrated that NOB were completely washed out. The control strategy was improved by the addition of two expert rules and stable operation was maintained even when external disturbances were provoked. Finally, a model-based study was performed to test the partial nitrification start-up strategy under different conditions and system configurations

Improvement of phosphate adsorption kinetics onto ferric hydroxide by size reduction

Ball milling and ultra-sonication size reduction procedures were applied to granular ferric hydroxide (GFH) to obtain two micro-sized adsorbents. These two adsorbents and GFH were investigated to improve the removal of phosphates from water. The size reduction procedures, using the milling method, allowed a reduction of size from 0.5–2 mm to 0.1–2 µm and total disaggregation of the GFH structure. Using an ultra-sonication method yielded a final size of 1.9–50.3 µm with partial disaggregation. The Langmuir model correlated well with the isotherms obtained in batch equilibrium tests for the three adsorbents. The maximum adsorption capacity (qmax) for the milled adsorbent was lower than GFH, but using ultra-sonication was not different from GFH. The equilibrium adsorption of two wastewater samples with phosphate and other anions onto the GFH corresponded well with the expected removal, showing that potential interferences in the isotherms were not important. Batch kinetics tests indicated that the pseudo second-order model fitted the data. Long-term adsorption capacity in kinetics (qe) showed the same trend described for qmax. The application of milling and ultra-sonication methods showed 3.5- and 5.6-fold increases of the kinetic constant (k2) versus the GFH value, respectively. These results showed that ultra-sonication is a very good procedure to increase the adsorption rate of phosphate, maintaining qe and increasing k2.Peer ReviewedPostprint (published version

La Tècnica FISH i el microscopi confocal aplicats a la determinació de fraccions de biomassa en un reactor aerobi nitrificant

Vegeu el resum del projecte de final de carrera en el document adjunt ResumPFCMarso