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%.     

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.     

The question of nitrification in the Passaic River, New Jersey: Analysis of historical data and experimental investigation

Historical NH₄⁺ and NO₃⁻ data from six stations on the Passaic River, New Jersey, were analyzed. The data for five of the stations span 1963 to 1976, and for the sixth station 1947 to 1976. Some of the conclusions reached are as follows:

1. (1) The concentration of NH₄⁺ fluctuated widely, but the trend was towards an increase with time.

2. (2) The concentration of NH₄⁺ was elevated during a period of extreme drought (1963 to 1966).

3. (3) The concentration of NO₃⁻ tended to increase smoothly with time.

4. (4) The concentration of NH₄⁺ increases longitudinally (with downstream travel).

5. (5) The loads (concentration × stream-flow) of both nitrogen species tended to increase with time.

6. (6) Substantial NO₃⁻ enters the stream from non-point sources.

7. (7) The potential for instream nitrification is not fully realized, as represented by elevated levels of NH₄⁺.

Item (7) was puzzling because conditions in the Passaic, especially in the summer, appear to be favorable for nitrification. The point was clarified, in part through an experimental investigation.River water samples, with and without added NH₄Cl, were incubated, and the course of the first step of nitrification was followed through the appearance of NO₂⁻. (The second step of nitrification was inactive during the experimental period.) The added NH₄Cl enhanced nitrification in samples from the uppermost stations (native NH₄⁺-N approximately 0.1 mg l⁻¹, but had little or no effect in samples from the middle and lower reaches (native NH₄⁺-N > 0.5 mg l⁻¹). Consequently, it was inferred that over most of the river's mainstem the growth of NH₄⁺-oxidizing bacteria was not substrate limited. There was also no indication of other nutrient limitations or of the presence of any inhibitors. This led to a projection of a 60-fold increase in the population density of planktonic NH₄⁺-oxidizers over a certain stretch of the river. However, no increase in the most-probable-number (MPN) of NH₄⁺-oxidizing bacteria was observed, which is consistent with item (7). In fact, at the end of a quiescent segment of the river the MPN's were anomalously low. This is attributed to the removal of cells from the water column through settling. This reasoning is extended to suggest that, throughout the river, settling may be the mechanism preventing a response of planktonic nitrifiers to the enrichment with NH₄⁺ from pollution sources. In turn, this could prevent a full expression of the potential for nitrification.The analyses are discussed from a regulatory perspective. It is concluded that the nitrification component of the Passaic's self-purification capacity is overburdened, and first became so in 1953.     

Application de l'analyse des correspondances a des resultats d'essais de traitement d'eaux de surface

Many results show that if a conventional coagulation-flocculation-clarification treatment line is combined with pre-ozonation, removal efficiency as regards pariculate and dissolved organics is substantially enhanced. However, research on the optimum balance between pre-ozonation and coagulation treatment has turned out to be difficult because of the numerous parameters that are involved. In order to identify the most significant among clarification criteria it was in fact necessary to develop a more elaborate model than is required for conventional statistical analysis, capable of comparing all the intervening factors. This we finally achieved by a program based on stepwise regression analysis.Measuring samples and parametersSamples. Samples were taken from the pilot plant located at Choisy-le-Roi on premises belonging to the Paris Suburbs Water Authority, over a period of 3 months from 1 April to 24 June, i.e. exactly 43 days of research.The plant shown in Fig. 1 consists of 4 trains working in parallel arrangement. This layout allows practically two complete treatment runs daily so that 8 different ozone-coagulations could be tested each day on the same quality of raw water. 387 samples were thus taken with 344 treated waters and 43 raw waters. The campaign was designed over this rather long period to achieve two ends:

1. (1) to gather enough results to give real significance to the mathematical computation. During the 43 day experimental campaign, each ozone-WAC combination was repeated more than 10 times;

2. (2) to find a means of allowing for fluctuation in the river in relation to phenomena of great amplitude such as rises in temperature and changes in flow rate, so that acquired results could eventually be extrapolated for application to industrial treatment plant management.

Parameters. Twenty-two parameters were measured in respect of each sample of raw and treated water. The aim of the research being to define the main parameters on which to base the combination, it was essential to begin with a study of all the magnitudes normally representative of suface waters.These parameters can be divided into various types:

treatment parameters: WAC + O₃; the concentration tested are shown in mg l⁻¹ in Table 2 and Fig. 2;

parameters concerning suspended solids: total number of particles per ml (NT) and their equivalent diameter (D), turbidity (Tu) expressed in drops of mastics and zeta potential (Z_p);

parameters concerning organics: total organic carbon (COT) in mg l⁻¹ of C, KMnO₄ in mg l⁻¹ of O₂, dissolved O₂ in mg l⁻¹, u.v. absorption at 254 nm, NTK and ammonia (NH₄⁺), both in mg l⁻¹.

Besides pH and temperature which vary very little in Siene river water, total aluminium (ALT) in mg l⁻¹ and residual ozone (RO₃) were monitored.Analysis of data. The basic data represented in the following matrix (I × J), in which I is the sum of the sampling steps and J the sum of the concentrations of the different chemical elements, are too vast for conventional statistical analysis. By factor analysis, one can obtain as a final result a geometrical figure in a two-dimensional space but that simultaneously accounts for all the combinations of I and J. We thus obtain a factorial chart analysing the proximity between variables in terms of correlation and that between individual points in terms of similarity of behaviour toward these variables as a whole.Each component i of I and j of J is represented in profile form ƒ_jⁱ (or ƒ_I^j)=k(i,j)/k(i) as shown in the matrix below:

Full-size image (1K)

All of the profiles and I and J, each with a volume allocated pro rata the complete line (or column), make up a set of points with a corresponding volume in a multi-dimensional space. In the case under study, each components i (sampling steps) are in a space with 22 dimensions and each variable j (concentrations) in a 387-dimensional space. The purpose of the analysis is to obtain from the cloud as true a representation as possible brought down to a 2-dimensional space. This dimensional reduction consists in finding a sub-space in which the space between individual points i or j are as close as posible to the initial distances in IR₂₂ (or IR₃₈₇). The distance used in factor analysis is the distribution distance expressed as: . The plane thus located is defined by 2 perpendicular straight lines. They are the factorial or inertia axes. Inertia measures the total dispersal area of the cloud on one axis and shows the ratio between the points projected in space and the sum of the square-roots of the distances between the initial points. It measures the dispersion of data on the axis. The axes are called “factors”.Using this method, it becomes possible to described the accumulated data and quantify the phenomena that control both the variable parameters and their components (I or J) without any preconceived hypothesis as to the relative importance of the initial data. And, furthermore, we have a simultaneous geometric representation of samples and variables.Results. The first (horizontal) axis, F₁ represent the abatement of suspended particles and organics. The second (vertical) axis enables the different treatment trains to be interpreted in terms of ozone and residual ozone. Four distinct groups appear on plane F₁ × F₂:

Group 1: Group 1 represents water with no WAC or ozone treatment nor residual ozone. Characteristics include a very high suspended particles content and a certain amount of organics (i.e. variables N, D₁, D₂…D₁₀ and KMnO₄). This group is representative of raw waters in general.

The variable KMnO₄ factor quite realistically reflects the clarification treatment, a high KMnO₄ value indicating the presence of raw water, a low content the presence of treated water.

Group 2: This is an intermediate group between raw water and the water in trains A and B. It is characterized by poor abatement of both suspended solids and organics and corresponds to the majority of waters in train D with no pre-ozonation and train A with low-rate ozonation (0.3 mg l⁻¹).

Group 3: A high WAC rate and an average ozone rate are the predominant features of this group in which residual ozone is very low. A good level of suspended solids and organic removal was obtained, as is the case of treatments in general, and as practically demonstrated by trains A and B.

Group 4: This group corresponds to the treated water with a high ozone injection rate, hence a high residual ozone content. A good level of suspended solids and organics removal is obviously obtained, most of the water having been treated on train C. This maximum ozone residual for a similar abatement of organics concentration indicates that the extra ozone added was in excess of the amount required in order to oxidize the quantity of organics in the effluent. The optimum ozone dose must therefore be somewhere near that of the previous group, i.e. trains A and B.

In conclusion, analysis by stepwise regression identified the five main variables that define the complete clarification process: N_T, KMnO₄, TOC, WAC and ozone. As regards the last two mentioned, differentiation between groups 3 and 4 provides a means of determining the optimum dose rate for ozone in the treatment concerned, i.e. less than for train C (group 3) where the residual ozone rate is higher, hence approximately the same as for trains A and B—in the region 0.3–0.8 mg l⁻¹.     

Restoration of heavily polluted branches of the Shatt Al-Arab river, Iraq

In view of the desire to improve the water quality of the heavily polluted branches of the Shatt al-Arab River at the City of Basrah, it was proposed to maintain effective flushing as well as contracting sewerage system. The present study was conducted in order to examine the water quality of these branches in an attempt to evaluate the effectiveness of the proposed flushing system. It has been found that their waters contained very low levels of dissolved oxygen and relatively high amounts of both COD and BOD₅. The annual average water quality parameters for Basrah Branches were: dissolved oxygen 3.4 ppm; pH 7.67; hydrogen sulphide 1.4 ppm; ammonia 97 μg-at. N l⁻¹; COD 15.9 mg l⁻¹; BOD₅ 12.7 mg l⁻¹; dissolved silicates 202 μg-at. Si l⁻¹; dissolved reactive phosphate 13.4 μg-at. P-PO₄³⁻ l⁻¹; nitrate 10.4 μg-at. N-NO₃⁻ l⁻¹; nitrite 2.1 μg-at. N-NO₂⁻ l⁻¹ and chlorophyll-α 14.3 mg m⁻³. Based on our calculations, it has been concluded that the proposed system is effective, thus within a flushing cycle all of the above mentioned parameters will become within the acceptable values of the Shatt al-Arab water quality. Moreover, this system has no appreciable effect upon the water quality characteristics of the Shatt al-Arab River due to the fact that it discharges a high volume of water annually. However, It has been recommended to dredge the deposited sludge to a minimum depth of 50 cm.     

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.     

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.     

The synthesis of the dissimilatory nitrate reductase under aerobic conditions in a number of denitrifying bacteria, isolated from activated sludge and drinking water

A number of denitrifying bacteria were isolated from activated sludge and drinking water. These bacteria were tested for the synthesis of the dissimilatory nitrate reductase under aerobic conditions (dissolved oxygen concentration above 4 mg · l⁻¹). The synthesis of this enzyme varied from total repression by oxygen in some bacteria, especially those isolated from drinking water, until a nearly non oxygen-repressed synthesis in other bacteria (strains 15 and N4). The effect of the dissolved oxygen concentration during growth of the bacteria on the synthesis of the dissimilatory nitrate reductase in cells of strain 15 was studied more extensively. A considerable repression of the enzyme synthesis was obtained when the dissolved oxygen concentration was relatively high (approx 15 mg·l⁻¹). Addition of chlorate to the growth medium of strain 15 (using NH⁺₄-N as nitrogen source) also resulted in a serious repression of the nitrate reductase synthesis during aerobic growth (dissolved oxygen above 4 mg·l⁻¹). The dissimilatory nitrate reductase of aerobically grown cells of strains 15 and N4 was found to be mainly localized in the membrane fraction.     

A mercury-free accelerated method for determining the chemical oxygen demand of large numbers of water samples by autoclaving them under pressure with acid-dichromate

In order to fulfill the objective of a water control program based on frequent sampling in several wastewater treatment plants, rivers and lakes a simplified method for measuring COD was developed. The procedure, in this article called the RR-method, includes: small sample and reagent volume; rapid addition of a mixture of all reagents to the sample; exclusion of mercury; autoclaving at 120°C for 1 h in flasks with fitted glass stoppers. To avoid dilution before analysis the method has been adapted for wastewater (I: 10–300 mg O₂ l⁻¹) and fresh water (II: 10–100 mg O₂ l⁻¹).Parallel analyses on different types of water samples according to Standard Methods showed that the yield by the RR-method was about 10% lower (Table 2). With water from the wastewater treatment plant at Uppsala (COD around 20 mg O₂ l⁻¹), the two methods gave an identical result. The somewhat lower yield was mostly due to decreased dichromate concentration and oxidation temperature. The lower oxidation potential made correction for chloride interference unnecessary below 1 g Cl⁻ l⁻¹ (Table 1).The RR-method also showed a good correlation to the values for KMnO₄-consumption. Parallel analyses of 318 samples from 14 wastewater receiving lakes gave the correlation coefficient r = +0.90 (Fig. 1).     

Conditions required for the precipitation of aluminium in acidic natural waters

Laboratory and field studies were carried out in order to define the conditions necessary for the precipitation of Al in natural waters of pH 4–6. It is concluded that if precipitation does occur it involves the formation of Al(oxy)hydroxide, not aluminosilicates or basic aluminium sulphates. The solubility product of the Al(oxy)hydroxide is highly temperature dependent (ΔH = −30.5 kcal⁻¹). It is also sensitive to concentrations of SO₄²⁻ and, more markedly, humic substances (HS); both of these decrease solubility, HS by more than an order of magnitude at a concentration of approx. 5 mg l⁻¹ (equivalent to approx. 2.5 mg l⁻¹ dissolved organic carbon). A semi-empirical equation is proposed that allows the prediction of the effective solubility product at different temperatures and at humic concentrations in the range 0–7 mg l⁻¹. Of the 113 natural water samples analysed, only one was calculated to be oversaturated with respect to Al(oxy)hydroxide.     

Effects of sodium and phosphate on growth of cyanobacteria

We conducted laboratory experiments to evaluate the effects of NaCl and phosphorus enrichments on natural phytoplankton assemblages from Lake Michigan in continuous-flow systems, at a dilution rate of 0.25 d⁻¹. The experiment was repeated four times, 1981–1982, using freshly-collected natural lakewater inocula and temperature regimes typical of near-surface waters at initiation (6, 12, 16 and 20°C), at two levels of PO₄−P (1–2 vs 91–92 μg l⁻¹) and of Na⁺ (3–4 vs 9–10 mg l⁻¹) each time. As a single factor, sodium chloride enrichments had no significant effect on growth rates or densities of cyanobacteria in cultures containing natural phytoplankton assemblages from Lake Michigan. However, filamentous cyanobacteria proliferated in the presence of elevated phosphorus concentrations, both with and without concurrent NaCl additions, particularly in warmer waters. Our laboratory results were consistent with the hypothesis that cyanobacteria are favored in phytoplankton of large lakes with low N:P ratios.     

Hypolimnetic aeration: field test of the empirical sizing method

A hypolimnetic aeration system was recently installed in a small (16 ha S_α) eutrophic lake and a comparison made between measured performance and predicted performance from an empirical sizing method. The design variables used to size the system were: hypolimnetic volume 451,600 m³; maximum hypolimnetic oxygen consumption 0.2 mg l⁻¹ d⁻¹; aerator input rate 2 mg l⁻¹; water velocity 0.76 m s⁻¹ and depth of air release 12.2 m. A 3.7 kW compressor (0.57 m³ min⁻¹) generated a water velocity of 0.46 m s⁻¹, a water flow of 17.7 m³ min⁻¹ and a theoretical hypolimnetic circulation period of 18 days. Dissolved oxygen increased by an average of 1.6 mg l⁻¹ on each cycle through the aerator, and aerator input rates ranged from 0.6 to 2.6 mg l⁻¹. Hypolimnetic oxygen consumption averaged 0.12 mg l⁻¹ d⁻¹ and ranged between 0.02 and 0.21 mg l⁻¹ d⁻¹. The aeration system was unable to meet the daily oxygen demand (90 kg) as the water velocity was slower than expected (0.46 m s⁻¹). To avoid undersizing future aeration installations the following recommendations should be considered when using the empirical sizing formula: (1) estimates of oxygen consumption should be annual maximums from aerobic hypolimnia; (2) aerator input rates should be conservative (e.g. 1–4 mg l⁻¹) and increase with depth; (3) water velocity of 0.45–0.50 m s⁻¹ should initially be used when no information on actual bubble size or velocity is available; (4) aeration start-up should be timed to avoid periods of accumulated oxygen demands.     

Acute and chronic toxicity of lead to rainbow trout salmo gairdneri, in hard and soft water

Lead was found to be highly toxic to rainbow trout in both hard water (hardness 353 mg l⁻¹ as CaCO₃) and soft water (hardness 28 mg l⁻¹. Analytical results differ greatly with methods of analysis when measuring concentrations of lead in the two types of water. This is exemplified in LC50's and maximum acceptable toxicant concentrations (MATC's) obtained when reported as dissolved lead vs total lead added in hard water. Two static bioassays in hard water gave 96-h LC50's of 1.32 and 1.47 mg l⁻¹ dissolved lead vs total lead LC50's of 542 and 471 mg l⁻¹, respectively. In a flow-through bioassay in soft water a 96-h LC50 of 1.17 mg l⁻¹, expressed as either dissolved or total lead, was obtained. From chronic bioassays, MATC's of lead for rainbow trout in hard water were between 18.2 and 31.7 μg l⁻¹ dissolved lead vs 120–360 μg l⁻¹ total lead. In soft water, where exposure to lead was initiated at the eyed egg stage of development, the MATC was between 4.1 and 7.6 μg l⁻¹. With exposure to lead beginning after hatching and swim-up of fry, the MATC was between 7.2 and 14.6 μg l⁻¹. Therefore, fish were more sensitive to the effects of lead when exposed as eggs.     

High-rate overland flow

Recommended loading rates for treating raw domestic wastewater by overland flow are 6.3–15 cm wk⁻¹. Information provided in the literature yields little insight regarding the upper range of hydraulic loading rates that could be effectively treated by overland flow. Therefore, field investigations were conducted to evaluate the performance of the overland flow system at overland flow rates from 0.95 m³ day⁻¹ m⁻¹ width of slope (13 cm wk⁻¹ to 4.15 m³ day⁻¹ m⁻¹ (57 cm wk⁻¹).Preliminary treated municipal wastewater was pumped to overland flow slopes, each approx. 3.7 m wide and 36.5 m long. The slope of each plot was 2.5%. The cover crop consisted of a mixture of ryegrass, bluegrass and fescue grass. The plots were operated for 2 years at six different hydraulic loading rates.Effluent BOD₅ concentration averages varied from 6 to 11 mg l⁻¹. The reduction of influent BOD₅ concentration ranged from 87 to 93%. Mean effluent suspended solids values were from 6 to 9 mg l⁻¹ with reductions of influent concentrations of 91–95%. Hydraulic application rate had little effect on percent BOD₅ or suspended solids removal.Total phosphorus reductions were minimal at all hydraulic application rates due to limited soil water contact.Ammonia concentration in the effluent ranged from 1 mg l⁻¹ NH₃-N at the 0.95 m³ day⁻¹ m⁻¹ (13 cm wk⁻¹) applied flow rate of 11.7 mg l⁻¹ NH₃-N at the 4.15 m³ day⁻¹ m⁻¹ (57 cm wk⁻¹) loading rate. Ammonia and nitrogen reductions decreased as the applied flow rate increased. Consequently, lower overland flow rates are necessary for nitrogen removal.The use of high-rate overland flow could potentially reduce the land necessary for this form of land application, if nutrient removal was not a local concern.     

The use of uric acid as a method of tracing domestic sewage discharges in riverine, estuarine and coastal water environments

The chemical tracking of sewage effluents discharged into fresh and saline waters presents difficulties, especially in estuaries. The main difficulty is caused by the dissolved constituents being used to monitor the effluent also occurring naturally at similar levels. Uric acid is present at significant levels in untreated sewage and is not normally found in unpolluted waters. Until now no suitable routine method has been available for uric acid estimation in fresh and saline waters at levels normally encountered in the environment. In this paper we describe a recently developed technique using high-performance liquid chromatography which estimates uric acid in both fresh and saline waters in the range 1–10,000 μg l⁻¹ with a precision (2σ) of ±20% at 2 μg l⁻¹, ±4% at 40 μg l⁻¹ and ±2% at 10 mg l⁻¹.     

Hyperconcentrated cultures of Scenedesmus obliquus: A new approach for wastewater biological tertiary treatment?

Algal cultures of Scenedesmus obliquus at low concentrations (0.1–0.2 g dry wt l⁻¹) provide adequate biological tertiary treatment of wastewaters. This research was aimed at studying the possibility of increasing the system performance by using hyperconcentrated cultures of S. obliquus (up to 2.6 g dry wt l⁻¹) at the laboratory scale. The algal culture grown on secondary effluent was first chemically flocculated with chitosan (30 mg l⁻¹) and decanted; the sedimented culture (5 g dry wt l⁻¹) was then resuspended in secondary effluent to obtain algal suspensions at various concentrations, the performance of which was compared to that of a control culture (0.13 g dry wt l⁻¹). The rate of exhaustion of nitrogen (N-NH₄⁺) was proportional to the algal concentration and a complete removal could be obtained within 15 min (at 2.6 g dry wt algae l⁻¹); this result compares favorably to the 2.5 h or so required by the control culture. The unit uptake rate for nitrogen (N-NH₄⁺) had a tendency to increase with the algal concentration, whereas that of phosphorus (P-PO₄³⁻) showed the opposite relationship. Considering the results obtained, it appears that hyperconcentrated algal cultures have a high potential for the tertiary treatment of wastewaters; a significant reduction of pond surface for large scale operations can be anticipated.     

Influence de sediments argileux incorpores au milieu d'insemination sur le succes de la fecondation chez la truite arc-en-ciel (Salmo Gairdneri)

The aim of this paper is to determine whether clay sediments suspended in water can prevent trout eggs from being fertilized. Kaolinite-rich clays (granulometric fraction: <2μm) (Fig. 1) were suspended in an artificial insemination diluent in doses ranging between 0 and 20 g l⁻¹. The eggs were exposed for 1, 10 or 20 min (experiment A) or inseminated (experiment B) in the diluent-sediment mixture. In experiment (C), the eggs were exposed to this mixture at three different temperatures (10, 15, 20°C). After insemination, the eggs were incubated for 10 days at 10°C and the percentage of eyed-eggs was used as an approximation of the fertility rate. The presence of clay sediments in the medium in which artificial insemination was carried out did not affect fertilization rate after the ovules had been exposed during 1 min to clay suspensions, at any of the temperatures used (8°C: Fig. 3; 10–15 or 20°C: Fig. 5) or at any of the sperm dilution rates (10⁻², 10⁻³, 10⁻⁴) (Fig. 3). On the contrary, there was a significant decline (P < 0.01) in the fertilization rate after the eggs had been exposed for 10 min at 8°C to doses of sediment exceeding 1.2 g l⁻¹ (Fig. 2). The fertilization rate also decreased significantly (P < 0.05) when the dose of sediment in the medium increased after 20 min at 20°C and 40 min at 15°C (Fig. 4). The 15 and 20°C temperatures were unfavourable for the eggs anyway. It is probable that fertility decreased due to micropyle clogging when the eggs were exposed longer than 10 min to the sediments. It is concluded that presence of sediments in the medium in which the gametes meet does not prevent fertilization.     

Influence of high NaCl and NH4Cl salt levels on methanogenic associations

The effect of high levels of NaCl and NH₄Cl on the activity and attachment of methanogenic associations in semi-continuous flow-through reactor systems has been evaluated. Two well-functioning reactors received shock concentrations of NaCl and NH₄Cl while two other reactors were adapted to increasing levels of the salts during a period of 45 days. The methanogenic associations, grown on a medium containing mainly acetate and ethanol, were found to be more resistant to NaCl and NH₄Cl than previously reported. Initial inhibition occurred at shock treatments of 30 gl⁻¹ for both salts. The reactors which were gradually exposed to increasing levels of the salts, adapted well and their tolerance levels surpassed those of the non-trained counterparts. Initial inhibition and fifty percent inhibition was observed at 65 and 95 gl⁻¹ respectively for adaptation to NaCl. Initial inhibition for the reactor adapting to NH₄Cl occurred at 30 gl⁻¹ and a 50% inhibition was observed at 45 gl⁻¹ of NH₄Cl. For the reactors receiving NH₄Cl, the free ammonia-N should be kept below a concentration of 80–100 mg l⁻¹ for optimal performance. The bacterial populations in the reactors consisted mostly out of Methanosarcina (> 99% of the biomass)     

Nitrate determination in fresh and some estuarine waters by ultraviolet light absorption: A new proposed method

The new proposed u.v./resin technique for nitrate determination is either not affected by, or can allow for, the following interfering chemicals at levels occurring in natural polluted or unpolluted waters; chloride, phosphate, sulphate, carbonate/bicarbonate, bromide, nitrite, coloured metal complexes, humic acids, ammonium, dyes, detergents, phenol and other u.v. absorbing organics. The method is quick and has an accuracy of ±3%. Concentrations of NO₃.N in the range 0.1–3.0 mg l⁻¹ can be determined in fresh water. Concentration of the sample to determine lower levels by evaporation is feasible with certain upland waters but should not be attempted if the sample has a high humic acid concentration. The technique can only be used in nitrate rich estuarine and coastal waters because the lower limit of detection is raised to 0.5 mg l⁻¹ when the sample is diluted to remove bromide interference.     

Investigation of the Folin-Ciocalteau phenol reagent for the determination of polyphenolic substances in natural waters

The methodology associated with the Folin-Ciocalteau phenol reagent was investigated and the performance characteristics of a method using sodium carbonate as the supporting medium were determined. Calibration curves using phenol, tannic acid, or l-tyrosine were linear up to at least 1000 μg l⁻¹. The limit of detection was 6 μg phenol l⁻¹ and the relative standard deviation at 100 μg phenol l⁻¹ was 5.2% and at 1000 μg phenol l⁻¹ was 4.1%. The absorbances obtained with equal amounts of a range of potential standards showed variations when compared with that of phenol: phenol (100%), l-tyrosine (62%), oak gall tannin (58%), tannic acid (48%), chestnut tannin (26%), oak tannin (24%), fulvic acid (5%). The method was applicable to a wide range of monohydric and polyhydric phenolic substances and interferences from inorganic and non-phenolic organic compounds were examined. Interference would be expected above 30 μg S²⁻ l⁻¹, 300 μg Mn(II) l⁻¹, or 400 μg SO₃²⁻ l⁻¹. Concentrations of iron >2 mg l⁻¹ as Fe(II) or Fe(III) formed the insoluble iron(III) hydroxide which increased the absorbance, but centrifugation could be used to remove this source of interference. Other potential sources of intereference (e.g. reducing agents and certain metabolic products) would be expected to have a negligible effect in unpolluted waters. Methods using diazotised sulphanilic acid or 4-aminoantipyrine (4-AAP) were found to be inferior when applied to natural water samples.