Dénitrification | EPFL Graph Search

La dénitrification, appelée aussi rétrogradation de l'azote minéral, est un processus microbien de respiration anaérobie qui utilise les ions nitrates comme accepteurs d'électrons. Ce phénomène biologique est opéré en milieu hypoxique ou anoxique, par des bactéries spécifiques qui satisfont leur besoin en oxydant par une désoxygénation des nitrates. Ce phénomène se produit dans le sol, mais pas exclusivement : il est aussi à l’œuvre dans certains sédiments, dans les aquifères (dans une certaine mesure et à certaines conditions), dans les matières organiques en décomposition (ex : bois mort), ou encore dans le système digestif. Importance écologique Ce processus joue un rôle majeur à échelle planétaire dans le cycle de l'azote, et est encore incomplètement cerné. Il est notamment l'un des "puits d'azote" comme il existe des puits de carbone. Il a fait l'objet de nombreuses études concernant ses aspects écologiques, agronomiques, microbiologiques, physiologiques, biogéoc

Atmospheric heterogeneous reactions of chlorine and bromine containing molecules

Arnaud Aguzzi

This thesis deals with a laboratory study of heterogeneous reactions involving bromine and chlorine containing reservoir species on alkali salt substrates which are relevant to the marine boundary layer, and on ice substrates which are relevant to the lower stratosphere. The aim is to obtain reliable data on uptake coefficients γ and reaction mechanisms for the sake of extrapolation of results obtained in the laboratory to atmospheric conditions. The experiments have been performed in a Teflon coated Knudsen flow reactor equipped with a quadrupole mass spectrometer. The reactions of BrONO2 with solid alkali halides have been studied at ambient temperature. The initial uptake coefficients γ0 of BrONO2 on NaCl and KBr substrates are γ0 = 0.31 ± 0.10 and γ0 = 0.32 ± 0.09, respectively. For NaCl substrates BrCl, Br2 and HCl and for KBr both Br2 and HBr are observed as products. HCl and HBr result from the interaction of NaCl and KBr, respectively, with HNO3 generated in the hydrolysis of BrONO2 with H2O condensed on the salt sample. Using NaCl we observed Br2 which is formed from heterogeneous BrONO2 decomposition occurring on solid KBr samples. Halogen exchange reactions are competing with hydrolysis and decomposition which also take place on non-reactive salts (NaNO3, Na2SO4). A high rate of initial uptake (0.2 ≤ γ0 ≤ 0.4) and a Br2 yield on the order of 50 % are observed on non-reactive salts with a closed mass balance for Br2. The ClONO2-salt system has been reinvestigated. Experiments on NaCl, KBr (reactive salts) and on NaNO3 and Na2SO4 (non-reactive salts) have been performed. The hydrolysis of ClONO2 was not observable in contrast to heterogeneous decomposition which occurred on non-reactive salts with a Cl2 yield of (25 ± 5) %. Calculations have been performed using a 0-D box model in order to observe the effects of heterogeneous chemistry on sea salt in the marine boundary layer. Chlorine and bromine chemistry is activated by heterogeneous reactions occurring on NaCl and KBr which are the sole sources of chlorine and bromine in the model. Simulations performed with chlorine heterogeneous chemistry and gas phase chemistry indicate: 1) Denitrification of the troposphere (NOy converted to solid nitrates). 2) Increase of the oxidative capacity of the troposphere by the release of Cl atoms. When bromine chemistry is added to the model, the recombination reaction of NO2 with BrO leads to an increase of tropospheric denitrification through formation of BrONO2. Calculations show that at high [NOx], the most important bromine reservoir is BrONO2, while at low [NOx] HOBr is the most important bromine reservoir. The uptake of HNO3 on ice, solid sulfuric acid solutions and solid ternary solutions (STS) has been investigated at 180 to 211 K. The uptake coefficient γ decreases from 0.30 at 180 K to 0.06 at 211 K. The Arrhenius representation shows two distinct regimes. The first at low temperatures (180-190 K) shows a constant value γ of 0.3, whereas the second regime at T > 195 K corresponds to an activation energy of Ea = -7 ± 1 kcal/mol. At a fixed temperature, γ is independent of [HNO3] thus confirming a rate law first order in [HNO3]. The γ values of HNO3 on H2SO4/H2O solid solutions linearly decreases from 0.20 (0.10) at 10 wt % H2SO4 to 0.05 (0.03) at 98 wt % H2SO4 at 180 K (200K). The γ values of HNO3 with STS of H2SO4/HNO3/H2O is equal to 0.10 ± 0.03 in the temperature range 185-195 K at conditions where the composition of the interface was held constant at the given temperature by adding an external flow of H2O. Br2O hydrolysis on ice surfaces occurs rapidly in the chosen temperature range of 180 to 210 K. At a fixed temperature the uptake kinetics follow an apparent first order rate law in [Br2O]. The observed negative temperature dependence leads to an activation energy Ea for heterogeneous hydrolysis of -2.3 ± 0.6 kcal/mol. These facts point towards a complex reaction mechanism implying that the interaction of Br2O with ice is not an elementary reaction. BrONO2 hydrolysis has been measured on bulk (B), condensed (C) and single crystal (SC) ice in the temperature range 180-210 K. On all types of ice, HOBr and Br2O are observed as products. At a fixed temperature the rate law is first order in [BrONO2] with γ ≈ 0.3 at 180 K. The observed negative temperature dependence leads to an activation energy Ea for the hydrolysis of BrONO2 on pure ice of -2.0 ± 0.2, -2.1 ± 0.2 and -6.6 ± 0.3 kcal/mol on (C), (B) and (SC) ice, respectively, pointing towards different kinetics of BrONO2 on these different types of ice. Doping the ice samples with HBr leads to the formation of Br2, preceded by BrONO2 hydrolysis. The Arrhenius representation corresponds to an activation energy of Ea = -1.2 ± 0.2 kcal/mol. We investigated the structural properties of the near-surface region of various types of HX (X = Cl or Br) doped ice. Basically, we studied the time dependent [HX] in the interface region using the fast reaction titration XONO2 + HX → X2 + HNO3. These experiments reveal that HX is located near the surface of the substrate in a well defined region of thickness I. The HX molecules composing the interface are immediately available for the titration reaction, whatever the flow of XONO2. In the temperature range 190-200 K, we measured a value of IHCl = 43 ± 16, 250 ± 50 and 444 ± 120 nm for (SC), (C) and (B) ices, respectively and IHBr = 110 ± 15 nm on (C) ice at 205K. Finally, we assessed the bulk diffusion coefficient for HX, DHX by modeling our results according to Fick's laws of diffusion. We obtained values of DHCl = 4.5·10-15 - 1.0·10-12 cm2/s at 190 K and DHBr = (6.5 ± 3.0)·10-15 cm2/s at 205 K.

EPFL2001

Epuration des eaux usées par lagunage à microphytes et à macrophytes en Afrique de l'Ouest et du Centre

Doulaye Koné

Stabilization ponds and water lettuce-based systems in West and Central Africa - State of the art, removal performances and design criteria Despite several projects undertaken so far, sanitation remains a huge challenge in West and Central Africa. Big cities are growing without sustainable solution for sanitation planning. Sewage systems and wastewater treatment plants are underdeveloped or absent. Stabilization ponds have been introduced 30 years ago, but this low-cost technology remains marginal in wastewater treatment systems. The climate context is favourable to develop a set of low-cost wastewater treatment plants, particularly macrophyte-based systems. Pilot scale studies show the enormous potentialities of such sustainable technologies for water pollution control and treatment. None of the full scale applications works and this is due to the low economic level and the lack of political support. Another important reason is the lack of training and research. This situation requires the development of a collaborative network in which African researchers can share knowledge and promote sustainable wastewater treatment plants, as sanitation demand is growing exponentially in conjunction with the population growth in the cities. Stabilization ponds account for only 7% of the whole wastewater treatment technologies built in West and Central Africa, against 75% of activated sludge processes that in most cases failed. In spite of their bad quality, the effluents are widely reused in urban agriculture. Experimental data showed a maximum removal rate of 30% and 60% for COD and BOD5, respectively, and a maximum loading rate of 500 kg BOD/ha/d. Macrophytes-based systems are even more scarce (3%). The link of this technology with potential risks of malaria has slowed down its development. Nevertheless, data from studies in Niamey and Yaounde, and from rice culture irrigation zones showed that this correlation is not significant. Little research is done on wastewater treatment technologies for local application. This is one more reason why this study was based at EIER in Ouagadougou (Burkina Faso). The aim of this work was to determine the parameters for optimal removal performance and to elucidate design criteria of water lettuce-based wastewater treatment systems, possibly in combination with stabilization ponds to promote restrictive irrigation in market gardening. In secondary treatment, the maximum admissible loading rate was found to be 500 kg BOD5/ha/d (400 mg O2/l). Above this value, sludge accumulation at the pond surface caused by intensive methanogenic degradation of the sediments lead to plants die-off. COD and BOD5 removal rate was not correlated to redox state or dissolved oxygen concentrations. This indicated that the removal was mainly due to settlement and trapping of suspended solids in roots and sediments. Aerobic degradation remains low because the extent of oxygen release by plants cannot explain the yield obtained. COD and BOD5 removal performance reaches an optimum rate of 75% and 85% in two weeks hydraulic retention time, respectively. Regression equations between applied (λappl) and removed (λrem) loads is expressed by λrem (COD) = 0.75λappl (COD) – 10.4, (r2 = 0.99). The first order kinetic constant for BOD5 removal, kT = 0.14 d-1 (or kT = 0.11 d-1 for the DCO) can be used for designing of treatment ponds with the equation from the International Water Association (IWA). From the total nitrogen entering the treatment ponds, depending on the nitrogen load, between 44% and 60% were removed in the configuration with three ponds and a HRT of 18 days. Nitrogen can be removed by plant uptake with the harvest, by settlement or trapping with the suspended solid or by elementary nitrogen formation which occurs by the combination of nitrification, denitrification, and anaerobic ammonium oxidation. Nitrogen removal by plants was estimated to account for 10% to 39% in total nitrogen removed from ponds with a HRT of 18 days based on the steady growing and nitrogen uptake rate found. With a weekly harvesting rate of 50% of total plant biomass in the ponds, the water lettuce growing rate and the nitrogen uptake were 50 ± 1 g dry weight/m2 (182.5 t dry weight/ha/year) and 0.36 g N/m2/d (1314 kg N/ha/year), respectively. Trapping and settling of organic nitrogen present mainly in the suspended solids fraction removed about 25-48% of total nitrogen. It was found that water lettuce-based treatment systems conserved quite large amounts of ammonium in the effluents, a fact that is favourable for irrigation water reuse. Nevertheless, nitrogen loss by nitrification-denitrification occurred in water lettuce ponds, and perhaps even anaerobic ammonium oxidation. Nitrification became visible when COD dropped below 140 mg O2/l. With nitrogen loading varying from 31 to 97 kg N-NH4+/ha/d, the ammonium removal rate varied from 15-40% with a HRT of 18 days and from 20-60% with a HRT of 21 days. Hence, 40-80% of the ammonium was conserved in the water lettuce-based systems. In addition to conserve ammonium, water lettuce ponds also perform better than facultative ponds in organic pollutant removal, 75% against 50% in DCO reduction, respectively. When discharging the facultative pond effluent in a water lettuce pond, removal performance of the combined (upgraded) system is equal to that of a water lettuce pond. Faecal coliform removal in the two systems is very close, three weeks were necessary to ensure a reduction of three logarithmic units in faecal coliform concentration. To reach the objective of irrigation reuse, water lettuce-based treatment plants should not significantly affect the availability of the treated water. It was shown that the additional water loss due to the presence of Pistia stratiotes is lower than 10% of the average evaporation rate of microphytes ponds. Based on the results obtained during this study the following recommendations can be made. If the surface occupied by a plant is a limiting parameter, the footprint of the ponds can be decreased by designing a water lettuce based system with ponds depth bigger than the recommended 70 cm. This depth has been proposed to promote oxygen release in ponds, which was supposed to support aerobic oxidation. According to our results, organic matter removal is not correlated to oxygen availability. In addition, increasing the pond depth could also increase the ammonium conserved in the effluent. For restrictive irrigation, in market gardening, a hybrid system combining facultative ponds with water lettuce ponds is suitable, not only to secure the effluent quality, but also to reduce constrains related to plant management. During this thesis, the beginning of a network for collaboration has been created between members of different research teams including the Abdou-Moumouni University in Niamey, the Cheick Anta Diop University of Dakar, the University of Yaounde and the Ecole Inter-Etats d'Ingénieurs de l'Equipement Rural (Ouagadougou) in Burkina Faso. Several topics investigated during this study should be studied in more detail, and this best within the framework of this network of collaboration in West and Central Africa.

EPFL2002

High plasticity of nitrogen fixation and denitrification of common coral reef substrates in response to nitrate availability

Nils Rädecker

Nitrogen cycling in coral reefs may be affected by nutrient availability, but knowledge about concentration-dependent thresholds that modulate dinitrogen fixation and denitrification is missing. We determined the effects of different nitrate concentrations (ambient, 1, 5, 10 μM nitrate addition) on both processes under two light scenarios (i.e., light and dark) using a combined acetylene assay for two common benthic reef substrates, i.e., turf algae and coral rubble. For both substrates, dinitrogen fixation rates peaked at 5 μM nitrate addition in light, whereas denitrification was highest at 10 μM nitrate addition in the dark. At 10 μm nitrate addition in the dark, a near-complete collapse of dinitrogen fixation concurrent with a 76-fold increase in denitrification observed for coral rubble, suggesting potential threshold responses linked to the nutritional state of the community. We conclude that dynamic nitrogen cycling activity may help stabilise nitrogen availability in microbial communities associated with coral reef substrates.

2021