A kinetic model for bioconcentration of lipophilic compounds by oligochaetes

Bioconcentration of lipophilic compounds by oligochaete worms has been modelled as consecutive partition equilibria, firstly between sediment and interstitial water and then between interstitial water and worm. Each interphase process has been assumed to proceed according to first order kinetics. The resulting expression for the biotic concentration as a function of time has been fitted to experimental data over the range 3 ≤ log K_ow ≤ 6 by varying the kinetic rate constants using a constrained, nonlinear least squares procedure. Relationships between uptake and clearance rate constants and log K_ow are in accord with existing theory. The regression equation between the equilibrium bioconcentration factor, K_B, and K_ow also is in general agreement with previous relationships established for other aquatic organisms. For many of the high K_owcompounds equilibration times are longer than can be reasonably achieved in laboratory experiments. The methodology presented has an advantage in that it does not require the establishment of equilibrium for the estimation of K_B, since the ratio of derived rate constants rather than biotic and water concentrations has been used.     

Investigations on natural Hungarian zeolite for ammonia removal

Use of natural zeolites deposited at Tokaj mountain, Hungary, for ammonia removal from synthetic and municipal wastewaters was studied. The optimal ion exchange conditions found were as follows: Na-form clinoptilolite, 0.5–1.0 mm in particle size and about 5–7 BV h⁻¹ loading rate. Using synthetic wastewater in the column of 9.5 cm i.d. × 92 cm, about 4.50 mg NH₃-N g⁻¹ clinoptilolite ammonia breakthrough capacity was achieved. For regeneration of the ion exchange bed, 10–20 BV of regenerant were necessary to remove the 98–99%, of ammonia with flow rate of a 5–7 BV h⁻¹.     

Towards a better understanding of high rate biological film flow reactor theory

On the assumption that performance of biological film flow reactors is independent of oxygen transfer, a theoretical extension of a mathematical model (after Ames) is described. This predictive and interpretive model incorporates both mass transfer-limitations between biomass and liquid film, and kinetic biological reaction rate of organic “food” utilization.Given general boundary conditions for the differential equations describing the mass transfer process, it is shown that: C_e = C_r + (C_l − C_r.exp(−K_m D/Q) where by definition: C_t = α C_s + C_r1/K_m = 1/K_LA_γ + α/Kx.For an influent concentration biochemical oxygen demand (C_i) and resultant effluent concentration (C_e) obtained during film flow through a packed media depth (D), the Model proposes that the residual concentration (C_r) is a function of surface irrigation rate (Q) and biomass activity. If this term is negative, adsorption occurs; while if positive, desorption from the biomass film at concentration (C_s) takes place.An overall mass transfer coefficient (K_m) is defined by a series equation where the usual mass transfer coefficient (K_L) is primarily a function of Reynolds Number [surface irrigation rate (Q) and specific surface area (A_V)], Schmidt Number (diffusivity of organic “Food”) and concentration. “Food” utilization at active sites on the biological film is governed by a specific adsorption coefficient (α) and explained by a Langmuir analogy. Biological conversion of “food” is described by a kinetic rate constant (K), while the necessary oxygen is defined by (X).This predictive model was developed from a wide range of pilot plant data, successfully tested further on a variety of published results and on actual full scale operating plants.Parameters derived from this Model, in terms of Height of Transfer Unit and Kinetic Reaction coefficient, characterize organic “treatability” for a variety of wastes.     

The adsorption of bovine serum albumin by activated sludge

The rapid removal, from suspension, of between 2–% of bovine serum albumin (BSA) by BSA acclimated activated sludge was attributed to adsorption. The extent of adsorption varied with the substrate to biomass (s/b) ratio. The concentration of BSA adsorped was influenced by both the concentration of BSA and the concentration of activated sludge. The experimental data did not conform to the calssical adsorption equations of Langmuir (J. Am. chem. Soc.40, 1361–1403, 918) or Freundlich (Colloid and Capillary Chemistry, Methuen, London, 1926) but to a newly developed equation, the activated sludge adsorption equation (ASAE). This new equation was tested and proven by experimental data and by data obtained independently by Banerji et al. (J. Wat. Pollut. Control Fed.40, 161–173, 1968) who investigated starch removal by activated sludge. Following the development of the ASAE, it was found possible to express both the concentration of BSA adsorbed per unit weight activated sludge (m) and the concentration of BSA in equilibrium per unit weight activated sludge (C/b) as a function of the concentration of BSA added to the system per unit weight adsorbent (C_t). Thus adsorption could be expressed as a function of the substrate to biomass (s/b) ratio.     

Uptake and release of zinc by aquatic bryophytes (Fontinalis antipyretica L. ex. Hedw.)

The zinc uptake and posterior release by an aquatic bryophyte—Fontinalis antipyretica L. Ex Hedw.—was experimentally studied in laboratory exposing the plants to different zinc concentrations in the range, 1.0–5.0 mg l⁻¹, for a 144 h contamination period, and then exposed to metal-free water for a 120 h decontamination period. The experiments were carried out in perfectly mixed contactors at controlled illumination, using mosses picked out in February 1997, with a background initial zinc concentration of 263 mg g⁻¹ (dry wt.). A first-order mass transfer kinetic model was fitted to the experimental data to determine the uptake and release constants, k₁ and k₂, the zinc concentration in mosses at the end of the uptake period, C_mu, and at the equilibrium, for the contamination and decontamination stages, C_me and C_mr, respectively. A bioconcentration factor, BCF=k₁/k₂ (zinc concentration in the plant, dry wt./zinc concentration in the water) was determined. A biological elimination factor defined as BEF=1−C_mr/C_mu was also calculated. BCF decreases from about 4500 to 2950 as Zn concentration in water increases from 1.05 to 3.80 mg l⁻¹. BEF is approximately constant and equal to 0.80. Comparing Zn and Cu accumulation by Fontinalis antipyretica, it was concluded that the uptake rate for Zn (145 h⁻¹) is much lower than for Cu (628 h⁻¹) and the amount retained by the plant decreased by a factor of about seven.     

Sorption and accumulation of cadmium in the sediment of the Tama River

Cadmium contents in the water and the sediment samples collected from the Tama River and several branches were measured. Cadmium (above 0.005mgl⁻¹) was detected in only four of the water samples, while the sediment samples showed cadmium content of 1.0–9.8 μg g⁻¹ dry sediment. Cadmium concentration in the sediments of the main stream was correlated against ignition loss of the samples and it was found that 1 g of ignition loss (organic matter) corresponded to 35 μg of cadmium.The batch adsorption experiment in the laboratory using an aqueous solution of cadmium for 14 sediment samples with a higher concentration of cadmium indicated that the amount adsorbed by the sediment is highly dependent on the ignition loss. The amount adsorbed on unit mass of ignition loss q_IL could be correlated by a Freundlich-type equilibrium relation as where C is the equilibrium concentration in the aqueous phase ranging between 7 × 10⁻³ and 10 mg l⁻¹, while k_IL and n are equilibrium constants.The adsorption rate measurement showed that the intraparticle diffusion coefficient of cadmium in the sediment was about 1.1 × 10⁻⁶ cm²s⁻¹, which is of a reasonable order of magnitude assuming the pore diffusion mechanism inside the particle.The results suggest that suspended solid particles of high organic content in flowing water contribute significantly to the transport of cadmium along the river.     

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.     

Predictive model for treatment of phenolic wastes by activated sludge

The current investigation was made to determine whether a model using cell recycle concentration as a major control parameter is applicable to inhibitory substrates such as phenol. Based upon preliminary studies, the Haldane equation was selected to relate specific growth rate and substrate concentration. Seven long-term pilot plant runs were made at different growth rates. Effluent and control parameters were measured frequently. The maintenance constant was obtained from the pilot plant data. The three Haldane equation constants and the true cell yield were estimated from pilot plant and batch data.The model gave satisfactory predictions with respect to biomass production (X and X_w) and effluent COD, based on the ΔCOD method. The predicted phenol concentration, although very low, was higher than the minute levels observed in the pilot plant effluent (±0.1 mg l⁻¹); possible reasons not directly related to growth are explored, e.g. retention of unmetabolized phenol in the sludge.     

Phosphates and ammonia recovery from secondary effluents by selective ion exchange with production of a slow-release fertilizer

A process for the reduction of eutrophic potential in urban secondary effluents. which comprises the selective exchange of phosphates on a weak anion resin and of ammonia on clinoptilolite, is described. Sodium chloride is used to regenerate both resins, with some Ca(OH)₂ added for clinoptilolite. By adding Mg(OH)₂, eventually precipitated with lime from sea water, the premium quality, slow-release fertilizer MgNH₄PO₄-6H₂O is recovered from the concentrated regeneration streams, which can then be recycled. Laboratory evaluations of the hydrolysis extent of the weak anion resin in the presence of bicarbonates showed that a steady-state is attained with resin exchange capacity reproducibly averaging about 80 mmol phosphates 1,⁻. The preliminary runs on a pilot plant for the tertiary treatment of urban sewage are also presented.     

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%.     

Some aspects of unsaturated flow in jointed rock

The applicability of Darcy's Law to two-phase flow has been discussed. Specialised triaxial equipment has been employed to separately inject two pore fluid components (air and water) into fractured rock specimens, so that two-phase flow behaviour can be studied at high axial and confining stresses. Improvements to recently developed two-phase high-pressure triaxial apparatus have enabled the authors to continue their study of air–water (i.e. unsaturated) flow in intact and fractured rock specimens under a wide range of stress conditions, similar to those encountered in underground mining operations. In this paper, a simplified stratified two-phase flow model is also presented that satisfactorily predicts flow behaviour in an inclined rock fracture over a range of linear laminar flow for particular capillary pressure relationships. The mathematical model is based upon the principles of conservation of mass and momentum, and relates the fracture aperture (e_t) to phase permeability (k_i) using Poiseuille's law and the proposed ‘phase height’, h_i(t), for water and air phases. The experimental approach used to verify the model predictions is described and the predicted results compared with the measurements. The experimental data confirmed the relationship between relative permeability and flow rate, with respect to two-phase flow conditions.     

Influence sur la cinetique biochimique de la concentration en carbone organique a l'entree d'un reacteur developpant une polyculture microbienne en melange parfait

Experiments were run in order to determine microbial growth kinetics of a mixed culture in a continuous stirred tank reactor using a multicomponent substrate. Analysis of the results indicated that effluent concentration does not depend only on the dilution rate but also on the concentration of substrate in the influent. A kinetic equation has been established using total organic carbon as a pollution indicator: k = k_o(S/S + αS_o)     

A comprehensive study on the biological treatabilities of phenol and methanol—I. Analysis of bacterial growth and substrate removal kinetics by a statistical method

An unbiassed statistical method was developed to evaluate kinetic parameters in the biological oxidation of wastewaters. Through the statistical analyses of the biological oxidation kinetics, it was shown that the kinetic equations satisfactorily described the bacterial growth and substrate removal kinetics where X is biomass concentration, S is substrate concentration, t is time, a is cell yield coefficient, k_d is cell decay coefficient, K_s is Michaelis-Menten constant, and k is substrate removal rate coefficient. The coefficients K_s and a changed with temperature insignificantly while k and k_d were closely related to it. The temperature independent coefficients K_s and a were estimated to be 236 mg 1⁻¹ (standard deviation, σ = 70 mg 1⁻¹) and 1.21 (σ = 0.06) respectively for phenol, and 2330 mg 1⁻¹ (σ = 1410 mg 1⁻¹) and 1.25 (σ = 0.45) respectively for methanol based on total organic carbon (TOC) and volatile suspended solids (VSS). The oxygen utilization rate can be formulated as where Rr is the oxygen utilization rate (mg 1⁻¹ O₂ time⁻¹), as′ is a coefficient designating oxygen requirement per substrate utilized, and b′ is a coefficient designating oxygen requirement per biomass for endogeneous respiration. The coefficient a′ was 1.39 for phenol and 2.23 for methanol, and b′ was 1.42 k_d for both substances based on TOC and VSS.     

An evaluation of pretreated natural zeolites for ammonium removal

Clinoptilolite has been widely studied for ammonium removal in the past 2 yr. However, many investigators have reported variations in the measured capacities of samples of clinoptilolite. These studies and the factors believed to influence measured zeolite capacity are reviewed. In addition no studies to evaluate other natural zeolites for ammonium removal have been reported.In this study samples of clinoptilolite, erionite, mordenite and phillipsite provided by the Anaconda Company were evaluated for ammonium removal from wastewaters. In addition, samples of clinoptilolite were pretreated in various ways to determine whether an improvement in ammonium removal performance could be realized. Total exchange capacities, capacities for ammonium removal from a synthetic waste, packed bed densities and crushing strengths were measured.Phillipsite was found to have almost twice the weight capacity for ammonium removal from synthetic waste compared to that of clinoptilolite. The volumetric capacity was 26% better than that of clinoptilolite. However, the phillipsite sample was extremely friable and it could not be used for water treatment unless it was strengthened with a binder.Pretreatment of clinoptilolite with NaOH, HNO₃ and steam did little to improve the zeolite's performance. However, heat pretreatment (600°C for 1 h) improved the zeolite's selectivity for ammonium significantly. Ammonium removal capacities were increased by approximately 17% for heat treated zeolite samples although the total exchange capacity of the zeolite was reduced somewhat.     

Effects of influent substrate concentration on the kinetics of natural microbial populations in continuous culture

In order to determine whether the influent substrate concentration exerts an effect upon the kinetics of soluble substrate removal by natural microbial populations growing in continuous culture experiments were run using a multicomponent substrate. A two-level factorial experimental design was employed with reactor dilution rate and influent substrate concentration as the independent variables. Analysis of the results indicated that both variables exerted a significant effect (1% level) upon the effluent soluble COD. It was possible to model the system using the linear approximation of the Monod equation resulting in an equation of the general form: S=K′S₀D + K″S₀The findings of the study indicate that engineers responsible for the design and operation of wastewater treatment facilities should consider the influent substrate concentration when choosing a mean cell residence time for the system.     

Equilibrium and kinetic ion exchange studies of Pb2+, Cr3+, Fe3+ and Cu2+ on natural clinoptilolite

In the present study ion exchange of Pb2+, Cu2+, Fe3+ and Cr3+ on natural clinoptilolite is examined at 27 +/- 1 degree C and initial concentration of 10 meq/dm3. Equilibrium is favorable for Pb2+, unfavorable for Cu2+ and sigmoid for Cr3+ and Fe3+. Selectivity series deduced from equilibrium isotherms is Pb2+ > Cr3+ > Fe3+ > Cu2+, while when maximum exchange levels (MELs) are considered, selectivity series is Pb2+ > Cr3+ approximately = Cu2+ > or = Fe3+. Cu2+ manifests the higher value of diffusion coefficient in the clinoptilolite particles among the metals studied, equal to 1.40 x 10(-9) cm2/s. According to the fixed bed experiments the upflow rate (5-15 Bed Volumes (BV)) is influencing the breakthrough point for all metals studied. The breakthrough point varies between 12.3 BV for Pb2+ and 1.18 for Cu2+. Flow rate is also influencing the operating capacity, giving values between 0.433 meq/g(clinoptilolite) for Pb2+ and 0.053 for Fe3+. Breakthrough point values confirm the selectivity order deduced from the equilibrium isotherms, while operating capacity values confirm the selectivity order deduced from MEL experiments.     

A rapid manual method for nitrate determination in small volumes by a modification of the cadmium reduction method

Nitrate concentration (2–100 μg NO₃-N1⁻¹) in water samples as small as 5 ml can be determined manually in test tubes by a modification of the standard cadmium reduction method without loss of sensitivity. Once reaction tubes are prepared, 30 samples can be batch-processed in one hour by this technique. Reaction tubes can be used 5–10 times before the reactivation of the cadmium is necessary.     

Effects of inhibitors on nitrification in a packed-bed biological flow reactor

The individual effect of trivalent arsenic, hexavalent chromium and fluoride on nitrification is studied under continuous load in a packed bed biological flow reactor. The results show that Michaelis-Menten rate expression gives the best representation of nitrification data in the absence of inhibitors. However, in the presence of inhibitors, the system follows a non-competitive mode of inhibition with the following rate expression: The values of V_max and K_s are estimated as 1.466 mg l⁻¹ min⁻¹ and 2.349 mg l⁻¹ respectively. The inhibitor constant K_i is evaluated as 273 mg l⁻¹ for trivalent arsenic, 56 mg l⁻¹ for hexavalent chromium and 1185 mg l⁻¹ for fluoride.     

Faut-il abandonner le formalisme de monod pour la modelisation des processus de depollution par voie biologique?

The use of Monod's model to express the velocity of depollution biological treatment is opposed by experimental evidence; it is impossible:

• to estimate the effects of the substrate concentration at the inlet on the substrate concentration at the outlet during a continuous fermentation;

• to obtain in certain cases positive values of the maximum growth rate during graphical determinations using the linearized form of the model;

• to estimate the variations of the saturation constant as a function of the sludge age and the biomass fraction in each tank in the contact-stabilization process.

The first two points have often been pointed out in literature and a review of the main publications on these subjects is supplied.The third point was mentioned during original research works on the contact-stabilization process, recently carried out by Saipanich and Yue. From Lawrence and McCarty's equation, it has been shown that Monod's model leads to a saturation constant K₃ which is not a true constant but depends on the sludge age and the total biomass fraction contained in the given tank.Yue proposes a new approach described by the equation: The fact that b may be superior or inferior to 1 makes it possible to explain the anomalies noted during the graphical determination of k₀.Like Contois's model, from which it is drawn, this model is compatible with a limitation of the growth by accumulating inhibiting metabolites in the culture medium. It also keeps the possibility to characterize the limitation of the culture by exhaustion of the substrate and to take into account the substrate transfer resistance surrounding the micro-organism, by considering the constant M as the sum of a saturation constant K₃ and a characteristic constant of the substrate diffusion resistance according to Powell.It is shown that this formulation generalizes the previous modeling processes by presenting Monod's, Contois's, Powell's, Elmaleh's classical models as particular cases corresponding to particular values of the constants used.This model is applied to different effluents and numerical values of the constants used are given. Objections to Monod's approach have not only appeared in the case of mixed cultures on complex substrate, but have also been raised by several authors in the case of pure cultures on simple substrate, when substrate is not dosed by specific analytical way but by a global analytical determination as BOD, COD or TOD.