Oxygenation par le peroxyde d'hydrogene des biomasses fixees utilisees en traitement biologique des eaux

Because of their advantages as compared to flocculated biomass processes, there is now a revival of interest in fixed biomass processes:no mishaps due to bad flocculation, particularly with filamentous organisms (bulking)compact equipment owing to the ability to obtain greater biomass concentrations (several g l⁻¹), which is impossible in flocculated biomass.In this paper, we will consider mainly bio-discs and submerged fixed bed filters. In bio-disc investigations, Hoehn and Ray's (1973), Kornegay and Andrew's (1968) now classical results showed that the bacterial film only acts on the surface, over a thickness which, at best, does not exceed 150 μm. At the same time, Bungay's (1969) very accurate measurements showed that the film active thickness coincides with the depth where the oxygen concentration in the film is higher than the critical oxygen concentration. In submerged filters, Elmaleh (1976) and Grasmick's (1978) theoretical studies permit one to define a Useful Column Height (UCH) which corresponds to the active part of the reactor and which is superposed on the height where oxygen concentration is higher than the critical oxygen concentration. In classical devices, the UCH is relatively low: approx. 0.50-1 m. In both cases, the system is provided with oxygen through an exchange between the air and the effluent to be treated, at a gas-liquid interface. This procedure limits the O₂ concentration to about 9 mg O₂ l⁻¹, at the ambient temperature. Therefore, to increase the UCH of a submerged reactor or the active thickness of a bio-disc film by increasing the oxygen penetrating depth, the oxygen partial pressure in the gas phase should be increased by either using pure oxygen or increasing total gas phase pressure.These two methods are somewhat difficult to use and we prefer to use another method: bringing dissolved oxygen directly into the liquid phase without the exchange at the gas-liquid interface. This is feasible by using an oxygen liberating labile chemical reagent i.e. hydrogen peroxide. We consider two types of fixed biomasses: the bio-discs and the submerged filters.Bio-discs. The apparatus used is shown in Fig. 1. The utilization of H₂O₂ resulted in a very sharp increase in the substrate removal efficiency. It is observed that the substrate removal efficiency (Figs 5 and 6) and the reduced pollution flux (Figs 4 and 7) show a maximum when these are plotted as a function of the ratio: equivalent quantity of O₂ given by H₂O₂/O₂ demanded by the effluent and as a function of dissolved oxygen in the liquid phase. Moreover, these curves suggest that oxygen acts as an inhibitor and different attempts at modeling, based on standard models of inhibiting effects, lead to the exponential model giving the lowest deviation (Fig. 8).Submerged packed reactors. The apparatus used is shown in Fig. 3. This unit is fed by urban effluents and the oxygenation in the reactor is carried out by using diluted H₂O₂ (0.5-1.5 N).     

Denitrification en continu a l'aide de microorganismes immobilises sur des supports solidesContinuous denitrification by immobilized cells

In this paper, we describe a study of biological denitrification by immobilized cells. Nitrates are reduced in sterile solutions by Pseudomonas aeruginosa immobilized in a fixed bed reactor, and in synthetic waste water by mixed cultures immobilized into a fluidized bed reactor.The fixed bed reactor is a Plexiglas column filled with corn stovers (Table 1). It is 0.05 m in diameter and 0.55 in height, its volume being approx. 11. The fresh medium is injected at the base of the column and the liquid level is regulated by an overflow weir. Reactor and carrier are sterilized with ethylene-oxide. After sterilization 1 l. of a growing batch culture of Pseudomonas aeruginosa is introduced aseptically and the reactor is then fed continuously (45 ml h^?1) with fresh medium (NNO₃ = 40 mg l^?1) until the first steady state is reached.Nitrates and nitrites are determinated by means of a colorimetric method.Reactor efficiency remains constant for over 40 days. Nitrates and nitrites concentrations are measured inside the reactor for flow varying from 2 to 16 ml min^?1 (Fig. 2). Reductions of nitrates and nitrites seem to be two first-order reactions (Fig. 3 and Table 2) and constant rate increases with flow rate (Fig. 4). Until nitrate concentration reaches 960 mg/l^?1 (NNO₃) degradation is correct (Figs 5 and 6), beyond nitrites, which have been formed, seem to be inhibitor.Using this reactor, 50 mg NNO₃ have been reduced per hour and per liter of empty reactor, but it may be possible to reduce 140 mg NNO₃ l^?1 h^?1 if fresh medium contains 200 mg NNO₃ l^?1.The fluidized bed reactor is a Plexiglas column filled with earthenware. It is 0.05 m in diameter and 3.15 m in height, its volume being approx. 6.201. Fresh medium is injected at the base of the column and the liquid level is regulated by an overflow weir. Figure 7 shows the retention time of the liquid in the reactor in relation to flow. The first steady state has been reached after 2 weeks, and it has not been possible to know half life time of the column.Four experiments were conducted (Table 3) and, for each nitrate, nitrite and methanol concentrations in the reactor were measured (Fig. 8). So, it appears that reduction of nitrates and nitrites are two first-order reactions (Table 4) and that constant rate values, which are higher than in fixed bed reactor, increase with flow.The reactor is more affected by a flow shift than by a nitrate concentration shift in fresh medium, and biomass linked onto carrier is about 76 mg of dry matter g^?1 of earthenware.So, our fluidized bed column is able to reduce 560 mg NNO₃ h^?1 l^?1 of empty reactor, then retention time of liquid is less than 3 min.     

Electroflottation et desinfection simultanee d'eaux residuaires urbainesSimultaneous electroflotation and disinfection of sewage

This reports presents the results of a simultaneous electroflotation and disinfection sewage treatment, after chemical coagulation and flocculation and in the presence of chloride ions at various concentrations. Theoretical studies had shown that anodic oxidation of chloride ions gives hyperchlorites (for pH 7.5) together with (if sufficient potential is provided) oxygen. A dynamic study was thus achieved. It appeared that for a given chloride concentration the chlorine production linearly increases with the current density and depends on the organic load (COD) and oxidation potential of the effluent (Figs 6, 7 and 8). The performances of the process were studied in the continuous mode on a small pilot plant, after treatment of the effluent with ferric chloride and an organic polymer (Fig. 2). In all experiments current density and chloride concentration were raised (respectively 100, 200, 300 A m^?2 and from 300 to 3000 mg l^?1). The results obtained showed that solid-liquid separation was improved over static clarification for 2 h (Table 3) and the disinfection efficiency was equal or better than that obtained with gaseous chlorine (Table 4, Fig. 9). For example at a 900 mg l^?1 chloride concentration the three current density used give treated water containing less than 10³/100 ml total coliforms (initial concentration 4.7 · 10⁷/100 ml). These results have direct applications to the design of electroflotation units where a better plug flow should be sought. Moreover this process produces highly concentrated sludges. The utilization of ATP (Adenosine Triphosphate) as an indicator of the viability of a biomass showed that the process is applicable to activated sludges with recycling. The experimental conditions required for this application are still uncertain and require further study.     

Essais d'aerateurs: Enseignements tires de 500 essais en eau claire effectues dans 200 stations d'epuration differentes—I. MethodologieTests on aerators: Conclusions drawn from 500 clean water tests conducted in 200 different sewage treatment plants—I. Test procedure

Aeration represents the main part of energy consumption in the activated sludge process and the evaluation of aeration systems efficiency is becoming more important, especially as energy cost increases. Since 1972, CEMAGREF teams have carried out more than 500 non-steady state clean water tests in sewage treatment plants. The first aim of these measurements was to compare the results collected in plants with those predicted by manufacturers.The distribution of the different types of aerators tested in the field by the CEMAGREF is given in Table 1. All tests are conducted using tap water under non-steady state conditions: the initial dissolved oxygen (DO) level is brought down to zero by adding cobalt chloride as catalyst and sodium sulfite. When all the sodium sulfite has been used, the increase in water dissolved oxygen content is monitored vs time in various places in the tank by means of membraned probes.The graphical procedure used for estimating the oxygen transfer coefficient (K_La) is shown in Fig. 1; this procedure is usually called “log deficit method”. The results are expressed for “standard conditions” (θ = 10°C; P = 760 mm Hg). The influence of temperature on oxygenation capacity is illustrated in Fig. 2.The water quality parameters that may affect oxygen transfer are investigated: it appears that only the presence of surfactants, flocculated suspended solids, or high salinity (conductivity > 1500 μS cm^?1—Table 2) are liable to have any appreciable effect on oxygen transfer. The unflocculated SS, pH and alkalinity have no effect on oxygenation results in the common range of values occurring in the tests (Table 3).Authors differ about the operational procedure in non-steady state clean water test. After 7 years' field-measurements the CEMAGREF teams have developed their own recommendations about test procedures; their main conclusions are the following:Dissolved oxygen analysis: the differences observed between the results ($\text{K}{}_{\mathrm{L}}\text{a}$) obtained simultaneously by Winkler titration of piped samples and those from in-tank probes never exceed 4% (Table 4). Reliable dissolved oxygen probes are suitable for accurate measurements of oxygen transfer.The number of sampling points should be no smaller than three for aeration tanks with a volume below or equal to 500 m³. It should be recommended to add one sampling point for every additional 500 m³.Location of sampling points requires attention. Differences may appear according to the locations of probes in the basin (Tables 5, 6 and 7).Sulfite pre-dissolution has no influence on results and should be avoided whenever possible.     

Utilisation de la clinoptilolite en potabilisation des eaux—elimination de l'ion NH4+Clinoptilolite in drinking water treatment for NH4+ removal

The objective of this study is to develop a technique to remove ammonium ion from water intended for potable purposes. An ion exchange method is used with a selective ion exchanger, a natural cation zeolite, clinoptilolite. Glass columns (Fig. 1) are used for laboratory experiments. These experiments show that the NH₄⁺ exchange capacity is very small compared to its total capacity 2.17 meq g^?1; its value depends essentially on the NH₄⁺ initial concentration and less on the Ca²⁺ concentration in the influent water. Figure 3 illustrates the practical exchange capacity relative to the initial concentration of ammonium ion for a soft water (Ca²⁺ = 35–50 mg l^?1). We were particularly interested in waters weak in ammonium ion concentration (NH₄⁺ = 1–3 mg l^?1). In this case and for ～1 and 2 mg l^?1 NH₄⁺ concentration in water, the practical capacity is only 0.06 and 0.108 meq g^?1 respectively. The leakage is smaller than the ECC limit (European Community Council) for drinking waters (NH₄⁺ ? 0.5 mg l^?1) and the treated volume of water to breakthrough, defined at 0.5 mg l^?1 of NH₄⁺, is ?720 BV (BV = bed volume) in both cases.In another way Fig. 6 shows that hard waters (due to Ca²⁺ ions) are more difficult to treat than soft waters. The practical capacity is smaller than before and the NH₄⁺-leakage is greater. To lessen NH₄⁺-leakage to less than 0.5 mg l^?1 for soft waters down-flow and up-flow, regeneration is used. Figure 7 shows that up-flow regeneration is more attractive than down-flow regeneration.Cycle reproducibility (Figs 4 and 5) shows that the regeneration conditions satisfied our requirements: in this case, the salt consumption is 180 eq of salt per eq of NH₄⁺ eliminated. This prompted us to try to reuse the regenerant (with NH₄⁺ ion). An increase of NH₄⁺-leakage is noticed in the presence of an NH₄⁺-residual in the regenerant. This increase is more significant with down-flow regeneration.After these laboratory experiments, we carried out a semi-industrial pilot-plant. Our objective was first to verify the laboratory results and secondly to study clinoptilolite behaviour relative to the time it was used. Two plexiglass columns comprise the pilot-plant shown in Fig. 9; soft water is used for these experiments. The first column is regenerated with fresh salt solution. The cycles obtained, considering their initial NH₄⁺-concentration, are reproduced in Fig. 10. For 2 mg l^?1 NH₄⁺ in the influent water, the leakage is about 0.2 mg l^?1 and the treated volume to breakthrough (0.5 mg l^?1 of NH₄⁺) is about 750 BV. The second column is regenerated with a recycled solution. The quality of the cycles decreases with the number of reuse of the regenerant as shown in Fig. 11. Nevertheless, it is interesting to note that after 3 reuses, the performance decrease is only 25% and the leakage, although it increases is smaller than 0.5 mg l^?1.Pilot results allowed us to propose a treatment of 30,000 m³ day^?1; the cost per cubic meter water treated, relative to NH₄⁺-removal, is about 0.165 FF (0.033 US $) for a plant and 0.77 FF (0.014 US $) for the same plant at the seaside. Using two serial columns decreased the cost by about 40–50%.     

Development of mathematical models for the treatment of an industrial wastewater by means of biological rotating disc reactors

In this study the extension of the mathematical model proposed by Grieves to experimental results obtained in the treatment of an industrial wastewater is examined. The laboratory-scale unit consists of three stages with seven discs per stage.The following conclusions are drawn: (1) the Grieves's model (originally derived for glucose solutions) is reliable also for an industrial wastewater; (2) within the range of organic loading of 8.7–27.7 g BOD₅ day⁻¹ m⁻², the diffusion of the organic substrate, through the liquid film adhering to the biological film, is the controlling step of the BOD₅ removal kinetics only when the disc rotational speed n is less than 0.6 rev min⁻¹; (3) for higher values of n, as those adopted for full-scale plants, bio-disc apparatus can be designed, with good approximation, by means of the Monod's equation, by considering the bio-disc unit as an idealized perfect mixing activated sludge reactor, whose volume and activated sludge concentration are equal to the volume of the active biological film and organism concentration in the same film.     

Denitrification en continu a l'aide de microorganismes immobilises sur des supports solides

In this paper, we describe a study of biological denitrification by immobilized cells. Nitrates are reduced in sterile solutions by Pseudomonas aeruginosa immobilized in a fixed bed reactor, and in synthetic waste water by mixed cultures immobilized into a fluidized bed reactor.The fixed bed reactor is a Plexiglas column filled with corn stovers (Table 1). It is 0.05 m in diameter and 0.55 in height, its volume being approx. 11. The fresh medium is injected at the base of the column and the liquid level is regulated by an overflow weir. Reactor and carrier are sterilized with ethylene-oxide. After sterilization 1 l. of a growing batch culture of Pseudomonas aeruginosa is introduced aseptically and the reactor is then fed continuously (45 ml h⁻¹) with fresh medium (N---NO₃ = 40 mg l⁻¹) until the first steady state is reached.Nitrates and nitrites are determinated by means of a colorimetric method.Reactor efficiency remains constant for over 40 days. Nitrates and nitrites concentrations are measured inside the reactor for flow varying from 2 to 16 ml min⁻¹ (Fig. 2). Reductions of nitrates and nitrites seem to be two first-order reactions (Fig. 3 and Table 2) and constant rate increases with flow rate (Fig. 4). Until nitrate concentration reaches 960 mg/l⁻¹ (N---NO₃) degradation is correct (Figs 5 and 6), beyond nitrites, which have been formed, seem to be inhibitor.Using this reactor, 50 mg N---NO₃ have been reduced per hour and per liter of empty reactor, but it may be possible to reduce 140 mg N---NO₃ l⁻¹ h⁻¹ if fresh medium contains 200 mg N---NO₃ l⁻¹.The fluidized bed reactor is a Plexiglas column filled with earthenware. It is 0.05 m in diameter and 3.15 m in height, its volume being approx. 6.201. Fresh medium is injected at the base of the column and the liquid level is regulated by an overflow weir. Figure 7 shows the retention time of the liquid in the reactor in relation to flow. The first steady state has been reached after 2 weeks, and it has not been possible to know half life time of the column.Four experiments were conducted (Table 3) and, for each nitrate, nitrite and methanol concentrations in the reactor were measured (Fig. 8). So, it appears that reduction of nitrates and nitrites are two first-order reactions (Table 4) and that constant rate values, which are higher than in fixed bed reactor, increase with flow.The reactor is more affected by a flow shift than by a nitrate concentration shift in fresh medium, and biomass linked onto carrier is about 76 mg of dry matter g⁻¹ of earthenware.So, our fluidized bed column is able to reduce 560 mg N---NO₃ h⁻¹ l⁻¹ of empty reactor, then retention time of liquid is less than 3 min.     

Études des transformations des formes du carbone, azote, phosphore, soufre et des principaux éléments minéraux au cours de la mesure de la demande totale en oxygene—III transformation des formes du soufre

Previous experiments carried out with the laboratory TOD meter Ionics 225 of the DOW Chèmical made it possible (after a high temperature catalytic action) to characterize the stable forms of organic and inorganic carbon and nitrogen (NH₄⁺, NO₂⁻, NO₃⁻), and the principal cations (Na⁺, K⁺, Ca²⁺, Mg²⁺) in the course of the total oxygen demand (TOD) measurement.The object of this study is firstly to compare the oxidation capability of different techniques of organic pollution (particularly the COD and TOD) in relation to the constituent elements of the organic matter C, N, P, S, and to calculate the possible interferences of the inorganic compounds at the time of TOD test.These investigations warrant the application of this technique to measure the amount of organic pollution in relatively mineralized conditions (Industrial wastewater, sea-water…). The present publication is concerned more with the study of the transformation of the organic and inorganic sulphur forms (S²⁻, SO₃²⁻. SO₄²⁻) in the course of the TOD measurement.The study of the oxidizability of the organic sulphur compound type C_xH_yO_zS, made it possible to establish a specific relation with a ratio of 0–50 mg of organic sulphur l⁻¹, between the oxygen demand of this element [TOD (S)] and its concentration (TOD (S) = 0.97 [S]).These tests showed a partial oxidation of the sulphur to SO₂ and SO₃ as the literature claimed. On the other hand, the oxidation of the same compounds during the COD tests varies greatly and although it is not possible to establish a correlation between these two measurements, as applies in the case of organic nitrogen, nevertheless these experiments showed a greater reliability of the TOD compared with the COD in the oxidation of organic matter in general. We then carried out experiments on the different mineral forms of sulphur in order to distinguish the possible effects and to recommend simple improvements.A relative study on sulphate ions had been carried out with standard solutions which have the same TOD (the basic TOD is obtained using potassium phthalate acid) and the same increasing concentration of the salt M₂SO₄ type. The experiments showed that the basic TOD decreases when the concentration of sulphate ions is increased (Fig. 3). Therefore, the interference is negative and taking into consideration the specific oxygen demand of the cation, we can propose an evaluation of this interference (ΔTOD (SO₄²⁻) = 0.203 [SO₄²⁻]). The same experiments have been conducted with a salt of M₂SO₃ type and similar results obtained (Fig. 5).The specific interference of the sulphite ion is negative and can be estimated by the following equation (ΔTOD (SO₃²⁻) = 0.132 [SO₃²⁻]). In both cases, we have to note that the transformation of these inorganic anions occurs between those relative to the theoretical dissociation reaction corresponding to the appearance of the oxide SO₂ and SO₃. For sulphurous on the contrary, the interference is positive and therefore corresponds to an extra oxygen demand (Fig. 8).The experiments were conducted directly with the M₂S salts (M representing K or Na) in aqueous solution.The evaluation of this interference had been made in the consideration of two concentration ranges of the sulphurous ions (0–35 mg S²⁻ l⁻¹): TOD (S²⁻) = 0.4 [S²⁻] and (35–100 mg S²⁻ l⁻¹): TOD (S²⁻) = 1.2 [S²⁻] − 30.Therefore this study confirms a better oxidation of the organic matter by TOD test in comparison with COD test.But sulphate and sulfite have a negative interference in the TOD measurement, whereas sulphurous is positive.The evaluation model of these interferences allows a correction to be made of the TOD value or to verify TOD measurement of organic pollution obtained by this technique.     

Adsorption de colorants ioniques sur le dechet lainier de carbonisageAdsorption of ionic dyes on wool carbonizing waste

Wool carbonizing waste is not used although large amounts are available in the countries where wool is processed. Wool carbonizing waste is made up of two components: the plant particles can be considered as sulfo lignins; the short-size wool fibres have undergone chemical modifications. Owing to its physical structure and to the polar as well as apolar properties of its macromolecules, this waste is liable to adsorb ionic organic solutes. The adsorption of ionic dyes on wool carbonizing waste was therefore investigated so as to evaluate its possible use for the decolourization of dyeing effluents. The effect of the solution-substrate reaction time on the adsorption at various temperatures was studied first. Temperature had a marked effect on the adsorption of the acid dye (AB 80) (Fig. 1) whereas the basic dye (BR 22) (Fig. 2) was characterized by its faster diffusion within the wool carbonizing waste particles. These differences can be ascribed to the higher steric hindrance of the AB 80 molecules and to their possible aggregation. The L-type adsorption isotherms corroborated the temperature effect already mentioned as well as the high affinity of the wool carbonizing waste with acid (Fig. 3) and basic (Fig. 4) dyes. The shape of the adsorption isotherms suggests that the adsorption proceeds through ionic bonding; as the dye molecules are oriented flatwise on the surface of the waste, the dye-substrate hydrophobic interactions can be maximum. The amounts adsorbed were 0.744 mmol g^?1 (i.e. 52.5%) for AB 80 at pH 2 and 0.193 mmol g^?1 (i.e. 5.5%) for BR 22 at pH 4. Higher amounts of basic dyes might however be expected to be adsorbed since the adsorption maximum is reached at pH 9 in the case of BR 22 (Fig. 5), as a result of the increasingly electronegative charge of the substrate. The Langmuir and Freundlich equations (Table 1) were used to have a mathematical model for the operation of a waste water processing unit. As shown by the L-type adsorption isotherms, the wool carbonizing waste used is suitable for the processing of low concentration effluents, such as dyeing waste waters: the decolourization of synthetic solutions was therefore considred. The column processing of an AB 80 solution showed the effect of the reaction time on the efficiency of the material used (Table 2). Investigation of the processing of a BR 22 solution in a stirred reactor led to the determination of the optimum carbonizing waste concentration (Fig. 6). as well as of the optimum effluent-substrate reaction time and the number of reactors to be used (Fig. 7). Eventually, the adsorptive power of the wool carbonizing waste used was compared with that of various materials (Table 3): the uptake capacity of wool carbonizing waste is lower than or equal to that of other substrates in the case of basic dyes but it is 6–10-fold higher in the case of acid dyes.     

Essais d'aerateurs: Enseignements tires de 500 essais en eau claire effectues dans 200 stations d'epuration differentes—II ResultatsTests on aerators: Conclusions drawn from 500 clean water tests conducted in 200 different sewage treatment plants—II Data interpretation

The large number of aerator tests conducted in the field by the CEMAGREF teams has allowed developing a critical review of tests results by means of statistical analysis. Measurement quality is estimated from the variation of the transfer coefficient values from one sampling point to another. Individual transfer coefficient values $\text{(}\text{K}{}_{\mathrm{L}}\text{a)i}$ are compared with the average value of the test $\text{(}\text{K}{}_{\mathrm{L}}\text{a). (K}{}_{\mathrm{L}}\text{a)i/}\text{K}{}_{\mathrm{L}}\text{a}$ ratios correlating with one year's data are gathered in histogramms (Fig. 1).A χ² test is used for evaluating the fit of a Normal distribution on each histogram (Tables 1 and 2 results for two kinds of surface aerators). When the Normality is not rejected, the variances between distributions are compared by means of a Fisher test.$\text{(K}{}_{\mathrm{L}}\text{a)i/}\text{K}{}_{\mathrm{L}}\text{a}$ variations in a same run are independent of transfer coefficient when the K_La ranges 1–10 h^?1 and applied specific power ranges 15–70 W m^?3. Those variations allow evaluating the technique of measuring, the reliability of oxygen probes and the operator's experience (Table 3).In a well mixed tank and when the recommended procedure is correctly implemented the relative error in measuring the specific oxygen input (kg O₂ kWh^?1) is 5%. In less favorable cases it reaches 10%.Tables 4 and 5 show the reproductibility of repetitive run results in the same plant and of tests performed with the same aerator in different plants.The histograms of the performances of the main types of mechanical surface aerators (high speed vertical shaft turbine, slow speed vertical shaft turbine, horizontal shaft aerator) are presented (Figs 2, 4, 5). Relations between oxygenation capacity and specific power consumption are plotted in Figs 3 and 6. As to other aeration systems, fewer data are available. Table 6 summarizes the usual range of performances.In 1974, after a series of measurements performed on 72 different plants, CEMAGREF stated that the oxygenation capacities claimed by manufacturers were, on the average, 40% higher than actual results. Now, the performances predicted by manufacturers in France are generally very close to the measured values. A difference higher than 10% between predicted values and measured ones now occurs as an exception.     

Microbial community distribution and activity dynamics of granular biomass in a CANON reactor

The application of microelectrodes to measure oxygen and nitrite concentrations inside granules operated at 20 °C in a CANON (Complete Autotrophic Nitrogen-removal Over Nitrite) reactor and the application of the FISH (Fluorescent In Situ Hybridization) technique to cryosectioned slices of these granules showed the presence of two differentiated zones inside of them: an external nitrification zone and an internal anammox zone. The FISH analysis of these layers allowed the identification of Nitrosomonas spp. and Candidatus Kuenenia Stutgartiensis as the main populations carrying out aerobic and anaerobic ammonia oxidation, respectively.Concentration microprofiles measured at different oxygen concentrations in the bulk liquid (from 1.5 to 35.2 mg O₂ L⁻¹) revealed that oxygen was consumed in a surface layer of 100-350 μm width. The obtained consumption rate of the most active layers was of 80 g O₂ (L_granule)⁻¹ d⁻¹. Anammox activity was registered between 400 and 1000 μm depth inside the granules. The nitrogen removal capacity of the studied sequencing batch reactor containing the granular biomass was of 0.5 g N L⁻¹ d⁻¹. This value is similar to the mean nitrogen removal rate obtained from calculations based on in- and outflow concentrations.Information obtained in the present work allowed the establishment of a simple control strategy based on the measurements of NH₄⁺ and NO₂⁻ in the bulk liquid and acting over the dissolved oxygen concentration in the bulk liquid and the hydraulic retention time of the reactor.     

Utilisation de la clinoptilolite en potabilisation des eaux—elimination de l'ion NH4

The objective of this study is to develop a technique to remove ammonium ion from water intended for potable purposes. An ion exchange method is used with a selective ion exchanger, a natural cation zeolite, clinoptilolite. Glass columns (Fig. 1) are used for laboratory experiments. These experiments show that the NH₄⁺ exchange capacity is very small compared to its total capacity 2.17 meq g⁻¹; its value depends essentially on the NH₄⁺ initial concentration and less on the Ca²⁺ concentration in the influent water. Figure 3 illustrates the practical exchange capacity relative to the initial concentration of ammonium ion for a soft water (Ca²⁺ = 35–50 mg l⁻¹). We were particularly interested in waters weak in ammonium ion concentration (NH₄⁺ = 1–3 mg l⁻¹). In this case and for 1 and 2 mg l⁻¹ NH₄⁺ concentration in water, the practical capacity is only 0.06 and 0.108 meq g⁻¹ respectively. The leakage is smaller than the ECC limit (European Community Council) for drinking waters (NH₄⁺ 0.5 mg l⁻¹) and the treated volume of water to breakthrough, defined at 0.5 mg l⁻¹ of NH₄⁺, is 720 BV (BV = bed volume) in both cases.In another way Fig. 6 shows that hard waters (due to Ca²⁺ ions) are more difficult to treat than soft waters. The practical capacity is smaller than before and the NH₄⁺-leakage is greater. To lessen NH₄⁺-leakage to less than 0.5 mg l⁻¹ for soft waters down-flow and up-flow, regeneration is used. Figure 7 shows that up-flow regeneration is more attractive than down-flow regeneration.Cycle reproducibility (Figs 4 and 5) shows that the regeneration conditions satisfied our requirements: in this case, the salt consumption is 180 eq of salt per eq of NH₄⁺ eliminated. This prompted us to try to reuse the regenerant (with NH₄⁺ ion). An increase of NH₄⁺-leakage is noticed in the presence of an NH₄⁺-residual in the regenerant. This increase is more significant with down-flow regeneration.After these laboratory experiments, we carried out a semi-industrial pilot-plant. Our objective was first to verify the laboratory results and secondly to study clinoptilolite behaviour relative to the time it was used. Two plexiglass columns comprise the pilot-plant shown in Fig. 9; soft water is used for these experiments. The first column is regenerated with fresh salt solution. The cycles obtained, considering their initial NH₄⁺-concentration, are reproduced in Fig. 10. For 2 mg l⁻¹ NH₄⁺ in the influent water, the leakage is about 0.2 mg l⁻¹ and the treated volume to breakthrough (0.5 mg l⁻¹ of NH₄⁺) is about 750 BV. The second column is regenerated with a recycled solution. The quality of the cycles decreases with the number of reuse of the regenerant as shown in Fig. 11. Nevertheless, it is interesting to note that after 3 reuses, the performance decrease is only 25% and the leakage, although it increases is smaller than 0.5 mg l⁻¹.Pilot results allowed us to propose a treatment of 30,000 m³ day⁻¹; the cost per cubic meter water treated, relative to NH₄⁺-removal, is about 0.165 FF (0.033 US $) for a plant and 0.77 FF (0.014 US $) for the same plant at the seaside. Using two serial columns decreased the cost by about 40–50%.     

Reacteur a cellules nitrifiantes immobilisees sur garnissage aere a co- ou contre-courant. Etude experimentale et modelisationNitrification by attached-cell reactors aerated at co- or counter-current. Experimental data and modelling

Attached-cell reactors using a bed of granular material for wastewater treatment develop a high biomass concentration which allows an important reduction of the required residence time (Jeris et al., 1977; Elmaleh, 1982). In nitrification of ammonia containing wastewater, oxygen is currently the limiting substrate; in theory, 4.18 g of oxygen are required per 1 g of nitrogen (Painter, 1970). Oxygen can be added with hydrogen peroxide (Grigoropolou, 1980; Seropian, 1980; Yahi et al., 1982) which is nevertheless expensive and it seems better to transfer oxygen from a gas phase, i.e. air, to the liquid phase through a fixed bed (Charpentier, 1976).Two attached-cell reactors (Fig. 1) were operated in parallel for nitrification of ammonia containing synthetic wastewater (Table 2). Air was upflowed through a granular packing (Table 1) maintained in fixed bed while the liquid influent was injected at co- or counter-current.

1. (1) Owing to the high oxygen transfer properties of the system and to the fact that the thickness of biofilm is always less than 100 μm, the whole process was not limited by oxygen concentration of which remained larger than 7 mg l⁻¹ (Fig. 2a) (Bungay et al., 1969). Oxidised nitrogen ammonia is completely converted into nitrate (Fig. 2b). Experimental conditions are given in Table 3.

2. (2) The plot of ammonia conversion against air superficial velocity shows a maximum (Fig. 3) after which conversion decreases rapidly by overloading of the packing (Prost, 1965). Experimental conditions are given in Table 4.

3. (3) Process efficiency decreases when superficial upflow velocity is increased (Fig. 4).

4. (4) Complete abatement of inlet pollution is reached when nitrogen concentration is less than 25 mg l⁻¹ (Fig. 5) which corresponds to a volumetric loading up to 0.6 kg N (NH₄⁺) m⁻³ day⁻¹.

Moreover, the experimental data were fitted to a model based on classical assumptions (Roques, 1980; Grady, 1982; Atkinson and Fowler, 1974; Grasmick et al., 1979; Grasmick, 1982; Harremoes, 1976, 1978; Jennings et al., 1976; Williamson and MacCarty, 1976); i.e. zero order intrinsic kinetics and diffusion transport (Table 5), and recently developed (Grasmick, 1982; Rodrigues et al., 1984). This model provides, particularly, a very easy method to check its own use—in reaction regime and in diffusion regime—when time spans or inlet concentration are changed; experimental results can indeed be plotted in such a way that straight lines are obtained (Table 6). Figures 6 and 7 show the data obtained with the counter-current nitrification reactor when respectively inlet concentration and time spans are varied. The plotted straight lines show that the overall reaction is zero order and that, therefore, the biofilm is fully penetrated. A critical time span θ_c and a critical inlet concentration C_c, for which complete conversion is achieved, are then calculated, θ_c is theoretically proportional to C₁ which is verified in Fig. 8. The straight line θ_c vs C₁ can then be used in reactor design.     

Adsorption des acides humiques sur charbon active en poudre. Influence du triphosphate de sodiumAdsorption of humic acids onto powdered activated carbon. The influence of sodium triphosphate

The use of activated carbon beds for the removal of natural humic and fulvic substances found in water supplies, has recently received considerable attention in water treatment operation (Lee et al., 1980; Le Cloirec et al., 1983). Moreover, the use of carbon adsorption for the reduction of haloform precursors (Anderson et al., 1981) and trihalomethanes produced by chlorination process, has contributed to a comprehensive investigation of adsorption characteristics of natural organic compounds (McCreary and Snoeyink, 1981). Many recent works showed the influence of adsorption system characteristics, such as pH, salt type, salt concentration and ionic heterogeneity in multicomponent adsorption systems, on the removal efficiency of humic and fulvic substances by activated carbon (McCreary and Snoeyink, 1980; Randtke and Jepsen, 1982; Weber et al., 1983). The purpose of this study is to examine the effect of a main component of domestic detergents, sodium triphosphate (STP), on the adsorptive capacities of powdered activated carbon (PAC) for commercially supplied humic acids, at different pH values in distilled water. Also, the effect of STP concentration and pH on the adsorption affinity of the PAC for humic acids, is discussed in relation with electrokinetic properties of carbon particles (zeta potential measurements).A first batch equilibrium study (Figs 1 and 2), showed an effective enhancement of adsorption capacity for humic acids as a function of STP concentration, in a non buffered media (pH of distilled water, close to 5.0). For example, visible absorption analysis of humic acids indicates an increase of 93% (500 mg l^?1 PAC) and 133% (1000 mg l^?1 PAC) in the carbon adsorption efficiency for a STP concentration from 0.2 to 1.0mM. A second batch equilibrium study (Figs 3 and 4) led to adsorption isotherms for humic acids in distilled water, as a function of STP concentration and initial pH value of the non buffered multicomponent system. Freundlich isotherms showed an increase in the adsorption capacity of the PAC for humic acids, with a decrease in pH and an increase in STP concentration. However, the adsorption capacity for humic acids is quite reduced at high pH values in presence of STP, in comparison with results obtained with distilled water.Electrokinetic measurements on PAC suspensions (Fig. 5) indicates that both humic acids and STP induce a negative variation of the zeta potential of carbon particles. In such a binary system, the zeta potential is a linear function of the pH; the negative surface charge of the carbon increasing with an elevation of pH (Fig. 6). Therefore, it appears that some adsorption of triphosphate polyanion from solution could occur, contributing then to the apparent negative surface charge of PAC particles.It has been previously showed that the type of anion in sodium salts, had little effect on the enhancement of adsorptive capacities of activated carbon for humic substances (Lafrance and Mazet, 1985), due to Na⁺ ions. However, adsorption of TP anions on the carbon surface may produce a source of repulsive charges, unfavourable to the co-adsorption of humic acids as the pH of the binary system reach more basic conditions. The influence of possible electrostatic interactions between adsorbates at the carbon surface, on the adsorption efficiency for humic acids, could then be studied by zeta potential measurements of PAC particles during the adsorption process.     

La diffusion intraparticulaire dans la clinoptilolite application aux ions Na+ et NH4+Intracrystalline self-diffusion of ions in clinoptilolite ammonia and sodium cations studies

Studies on NH₄⁺ removal by mean of a zeolite: clinoptilolite, previously realised have led the authors to examine the exchange mechanisms between cations on the clinoptilolite grains.The use of clinoptilolite as conventional ion exchange resin (1, 2, 3, 4, 5, 6) for elimination of ammonia ion from waste waters or drinking water (7, 8, 12) poses a great number of difficulties, principally during regeneration.This text presents a brief theorical presentation of the material and the ion-exchange, especially in the case of isotopic exchange, allowing the introduction of the fundamental equation (2) and its approximate expression:

$\text{U(t)}\text{1?exp}\text{?}\text{D}\text{tπ}{}^2\text{r}{}^2{}_0{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$

with U(t) the exchanged fraction at time t.The experimental study concerns the NH₄⁺ cation exchange with Na⁺ ions on clinoptilolite.In this case, the curve u(t) and ln(l ? u²) vs time shows the non-applicability of the above formula (Fig. 5).Our subject was to examine the divergence causes and to propose for our regeneration problem a semi-empiric law which form is:

$\text{U(t)}\text{1?exp}\text{?}\text{β}\text{D}\text{tπ}{}^2\text{r}{}^2{}_0{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$

with

$\text{β=[1?U(t)]}\text{2}\text{3}$

.The validated relation (Fig. 7) for the Na⁺/NH₄⁺ exchanges lead us to find the D_Na⁺ and D_NH2⁺ coefficients consistent with the literature.Using the experimental results from AMES, we show that our formula can be applied to other exchange cases (e.g. Sr⁺/NH₄⁺) (Fig. 8). The form of the β relation seems coherent with the proposed film diffusion interpretation.     

Methode rapide de dosage selectif des chlorophylles a et b utilisation de la separation par chromatographie liquide haute pressionA selective and rapid method of chlorophylls a and b separative determination by high-pressure liquid chromatography

The usual extraction methodology of the phytoplankton chlorophylls by acetone at 90% and their usual detection by spectrophotometry of the global extract at different wave lengths seem to be insufficient to many authors. With intent to improve this method (extraction, detection), we have verified first that methanol extraction was more effective than 90% acetone extraction, and we have set up a method of detection as simple and rapid as the usual one but which allows measuring the chlorophylls quantitatively and specifically, once they are separated. The chlorophylls a and b were separated by high-pressure liquid chromatography in reversed phase with a spherisorb ODS C₁₈ column eluted with methanol-water ($\text{97}\text{3}$) at a flow-rate of 1 ml min^?1; after being eluted they were detected by spectrofluorometry (excitation 427 nm and detection 470 nm) (Figs 1 and 2). This selective, sensitive rapid (20 min) determination can be automated by using an automatic injector and the recording on an integrator. The standardization of chlorophylls a and b was carried out with fluoranthen (internal standard) which does not want preparing again at every set of determinations (Fig. 3). This is a great advantage when we consider the fast degradation of the standards. This method allows using absolute methanol which is an extracting solvent more efficient than acetone 90% in the specific case of Scenedesmus subspicatus, whose pigments are known not to be easily extracted, and, in a broader sense, in the case of natural phytoplanktonic populations. To add BaCO₃ as a basic material during extraction is not recommended. This methodology may be used for biomass estimates by routine analysis as well as for the delicate measuring of pigments. Chromatographic profiles of Scenedesmus subspicatus extract and Seine river extract are presented in Figs 4 and 5.     

Essais d'aerateurs: Enseignements tires de 500 essais en eau claire effectues dans 200 stations d'epuration differentes—I. Methodologie

Aeration represents the main part of energy consumption in the activated sludge process and the evaluation of aeration systems efficiency is becoming more important, especially as energy cost increases. Since 1972, CEMAGREF teams have carried out more than 500 non-steady state clean water tests in sewage treatment plants. The first aim of these measurements was to compare the results collected in plants with those predicted by manufacturers.The distribution of the different types of aerators tested in the field by the CEMAGREF is given in Table 1. All tests are conducted using tap water under non-steady state conditions: the initial dissolved oxygen (DO) level is brought down to zero by adding cobalt chloride as catalyst and sodium sulfite. When all the sodium sulfite has been used, the increase in water dissolved oxygen content is monitored vs time in various places in the tank by means of membraned probes.The graphical procedure used for estimating the oxygen transfer coefficient (K_La) is shown in Fig. 1; this procedure is usually called “log deficit method”. The results are expressed for “standard conditions” (θ = 10°C; P = 760 mm Hg). The influence of temperature on oxygenation capacity is illustrated in Fig. 2.The water quality parameters that may affect oxygen transfer are investigated: it appears that only the presence of surfactants, flocculated suspended solids, or high salinity (conductivity > 1500 μS cm⁻¹—Table 2) are liable to have any appreciable effect on oxygen transfer. The unflocculated SS, pH and alkalinity have no effect on oxygenation results in the common range of values occurring in the tests (Table 3).Authors differ about the operational procedure in non-steady state clean water test. After 7 years' field-measurements the CEMAGREF teams have developed their own recommendations about test procedures; their main conclusions are the following:Dissolved oxygen analysis: the differences observed between the results ( ) obtained simultaneously by Winkler titration of piped samples and those from in-tank probes never exceed 4% (Table 4). Reliable dissolved oxygen probes are suitable for accurate measurements of oxygen transfer.The number of sampling points should be no smaller than three for aeration tanks with a volume below or equal to 500 m³. It should be recommended to add one sampling point for every additional 500 m³.Location of sampling points requires attention. Differences may appear according to the locations of probes in the basin (Tables 5, 6 and 7).Sulfite pre-dissolution has no influence on results and should be avoided whenever possible.