The elimination of sulfur dioxide interference in the low level chemical oxygen demand analysis

Sulfur dioxide is a reduced compound which acts as a positive interference in the chemical oxygen demand (COD) analysis. Significant amounts of sulfur dioxide present in industrial waste samples may therefore result in erroneously high COD values, compared to that of a sample with only the organic portion of the waste. By adding 65 mg l⁻¹ Mn²⁺ to a secondary wastewater sample spiked with 500 mg l⁻¹ sulfur dioxide, and oxygenating the sample for 6 min, sulfur dioxide was oxidized completely to sulfate. This oxidation procedure provides a statistically valid means of removing SO₂ interference in the COD analysis. The procedure provides an efficient means of investigating the organic COD of industrial effluents laden with SO₂ or its dissociation products.     

Etudes des transformations des formes du carbone, azote, phosphore, soufre, et des principaux elements mineraux au cours de la mesure de la demande totale en oxygene—I. Transformation des formes du carbone et des principaux cations

Les expériences réalisées sur le D.T.O. mètre de laboratoire IONICS 225 de la Dow Chemical, ont permis de caractériser, aprés l'action catalytique à haute température, les formes stables du carbone, de l'hydrogéne et des cations sodium, potassium, calcium, magnésium.Dans l'intervalle 0–250 mg O₂ l ou la réponse du capteur d'oxygène est proportionnelle à la concentration en matière organique nous avons démontré expérimentalement que le carbone organique ou minéral est transformé en CO₂ l'hydrogène en H₂O, et les cations sodium, potassium, calcium, magnésium en leurs oxyde et hydroxyde correspondants.Les ions bicarbonates et carbonates sont réduits et créent une interference négative: par contre les cations sont oxydés et creent une interférence positive dans la mesure de l'équivalent oxygéne par le D.T.O. métre.     

Toxicite des eaux de ruissellement de la fonte de neige en milieu urbain

There is a current paucity of information on the characteristics of water originating from melting snow in urbanized areas. In fact no data exist on the potential chronic toxicity of waters originating from melting snow combined with sewage waters of industrial and domestic activities. Bioassays were conducted on the green alga Selenastrum capricornutum to evaluate the composite effect of all pollutants occurring in waters originated from melting snow in urbanized areas and also to determine the long-term bioavailability of selected toxicants in these waters.The publication resumes a sampling study of two outfalls (Curotte-Papineau and Meilleur-Atlantique) from collector systems on the island of Montréal, Québec, Canada (see Fig. 1). Both sewer systems are of the combined surface runoff-wastewater type, are self contained and drain watersheds of 11.7 and 22.2 km² area respectively (see Table 1). The sampling program carried out in spring (March–May) 1978, was oriented towards the analysis of flow-quality relationships during two dry and three snowmelt periods. The flow from the intrusion of snowmelt into the sewage networks were due not only to high air temperature and solar radiation conditions but also to a heavy rainfall (9.67 mm; maximum intensity of 4.6 mm h⁻¹. The principal water quality parameters studied were BOD₅, COD, Cl⁻, N_in, P_i, Pb, Cr, Zn, Cn⁻ and SS (see Table 2).In addition a bioassay based on the fertility potential [the Selenastrum capricornutum Printz algal assay bottle test; U.S.E.P.A. (1978)] on filtered samples (1.2 μm GF/C) of waste water was used to detect any toxological qualities of the outfalls during both dry and snowmelt periods. An analysis of the relationship between chemical quality and the toxological properties of the samples from both sewage networks showed that water collected during a period of snowmelt without rain had a greater potential chronic toxicity and greater mean ratios of B_EDTA/B than combined water collected during a dry climatic period (see Table 3). This toxicity is due mainly to inorganic compounds. However, the increase in water discharge rate during periods of snowmelt accompanied by rain results in an apparent dilution of the aquatic toxicants. The potential chronic toxicity of water during the latter periods is consequently reduced compared with combined waters during dry periods.Knowledge of relationships between water flow and the chronic toxicity characteristics of waste water from urban snowmelt is necessary in the planning of any future combined water treatment system.     

Mode d'action du bioxyde de chlore sur les composes organiques en milieu aqueux: Consommations de bioxyde de chlore et reactions sur les composes phenoliques

The aim of our work was to study the reaction between chlorine dioxide (ClO₂) and organic substances. In the first part of our survey, chlorine dioxide demands were measured in diluted aqueous solutions of various kinds of organic compounds (5 × 10⁻⁵ −10 M) at pH 7. In the second part, the study of the action of chlorine dioxide on phenols (phenol, di and triphenols) was undertaken by observing the change of the organic substance through global parameter controls (COT, u.v. spectrum) and by trying to identify a certain number of oxidation products by means of chromatographic analysis (HPLC and GC), of mass spectrometry and of Nuclear Magnetic Resonance spectrometry (NMR).     

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—II. Transformation des formes de l'azote

The experiments realized with the laboratory T.O.D. meter Ionics 225 the DOW Chemical have allowed to distinguish, the stable forms of organic and inorganic nitrogen, after high temperature catalytic action. Organic and ammoniacal nitrogen are partially oxidized during the T.O.D. measurements whereas in the classic C.O.D. and B.O.D.₅ tests these forms are oxidized incompletely. Nitrous and nitric nitrogen induce negative interferences, which can be evaluated and corrected by graphical corrections.     

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%.     

The role of pH on the acute toxicity of sulfite in water

The toxicity of sulfite to fish decreases with increasing pH value, because the HSO⁻₃ ion is more toxic than the SO²⁻₃ ion. An effective sulfite concentration S_eff which is proportional to the toxicity on fish, is expressed by the following equation: S_eff=[HSO⁻₃]+ƒ[SO²⁻₃]where ƒ is a coefficient which expresses the change of toxicity of sulfite depending on the pH of the water, and varies for each species of fish. For goldfish, owing to the very small toxic contribution of SO²⁻₃ ion (ƒ = 0·07), the pH dependence of the toxicity of sulfite on pH was so strong that sulfite seemed almost non-toxic in basic solution. However, ƒ for guppy is somewhat larger (ƒ = 0·20) so that the toxicity of sulfite weakly depends on the pH value of water.     

Input–output analysis of macroelements in ICP-IM catchment area, Estonia

Using bulk deposition, throughfall, stemflow, soil infiltration, runoff water, litterfall data, ion mass budgets were calculated for a catchment area and for mature spruce and pine stands on it. The ions considered in mass balances were Na⁺, K⁺, Ca²⁺, Mg²⁺, SO₄²⁻, NO₃⁻, NH₄⁺, HCO₃⁻, and H⁺. Corresponding fluxes for the budgets were calculated as an average for 6 years of studies (1995–2000). Annual input–output balances of all nutrients were positive at the plot-scale, so that leaching into soil water was less than the corresponding deposition load. Deposition of Ca, Mg, Na and S into soil by precipitation exceeded input through litterfall. A proton budget approach shows that the main soil buffering process is retention of sulphate, which clearly exceeds weathering. At the catchment-scale, input–output analysis shows essential output of cations due to weathering from the soil. A distinct change in input–output balance of sulphate during study period was evident. The retention of sulphur has been replaced by its release from the catchment area.     

Rate constants of reactions of ozone with organic and inorganic compounds in water—III. Inorganic compounds and radicals

Second-order rate constants for reactions of ozone with 40 inorganic aqueous solutes are reported. Included are compounds of sulfur (e.g. H₂S, H₂SO₃, HOCH₂SO₃H), chlorine (e.g. Cl⁻, HOCl, NH₂Cl, HClO₂, ClO₂), bromine (e.g. Br⁻, HOBr), nitrogen (e.g. NH₃, NH₂OH, N₂O, HNO₂) and oxygen (e.g. H₂O₂), as well as free radicals (e.g. O₂⁻, OH^•). Most of these compounds exhibit an increase in rate constant with increasing pH corresponding to their degree of dissociation. Rate constants are based on ozone consumption rates measured by conventional batch-type or continuous-flow methods (10⁻³-10⁺⁶ M⁻¹ s⁻¹ range) and determinations of stoichiometric factors. Also listed are data determined by pulse-irradiation techniques using kinetic spectroscopy (10¹⁰ M⁻¹ s⁻¹ range). Additional literature data are reviewed for completeness. Results are discussed with respect to water treatment and environmental processes.     

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).     

Chloration de composés organiques: demande en chlore et réactivite vis-a-vis de la formation des trihalométhanes. Incidence de l'azote ammoniacalChlorination of organic compounds: Chlorine demand and reactivity in relationship to the trihalomethane formation. Incidence of ammoniacal nitrogen

The purpose of this work is to contribute to knowledge of the condition of formation of volatile and non-volatile organochlorinated compounds during surface water chlorination. With this aim in view, the chlorination of a number of organic substances in diluted aqueous solutions (10⁻⁶-10⁻⁵ moll ⁻¹) and in a neutral medium was studied. Special attention was given to their reactivity in relation to the formation of trihalomethanes.The results obtained show great differences in the reactivity of chlorine towards chemical substances liable to be present in the waters. The high chlorine demands, 5–12 mol of chlorine per mol of compound after a 15 h reaction at pH 7, where obtained with those aromatic compounds having activating groups such as — OH and — NR₂ (phenol and aniline derivatives). On the other hand, a number of compounds (alipahitcs in general; acids, aldehydes, alcohols…) are relatively inert towards chlorination.As far as chloroform production is concerned, the study shows that many organic compounds are liable to lead to the production of low quantities of chloroform in a neutral medium (molar yields < 5%). However, only a few specific structures such as metapolyhydroxybenzenes and metachlorophenols constitute good precursors of the haloform reaction.The study of the formation kinetics of chloroform, carried out with some precursors of different reactivity: acetone, acetylacetone, resorcinol, phloroglucinol and 3,5-dichlorophenol allowed us to determine the kinetic constants of chloroform formation at pH 7.5 and 20° C:

The results obtained during this work also show that the chlorine found in the chloroform produced from a precursor, represents only a small proportion of the chlorine demand. Even with a highly reactive precursor such as resorcinol. It was shown that the liberation of chloroform is accompanied by the formation of trichloroacetic acid (molar yield < 10%) and of monochloromaleic acid (molar yield 60%). Moreover, tetrahalogenated and pentahalogenated hydrocarbons (C₃Cl₄ and C₃ HCl₅) resulting from 3,5 -dichlorophenol chlorination were made manifest. As for the chlorin- ation of acetylacetone, a mechanism passing through the formation of 1,1-tri- chloroacetone was proposed.Lastly, in the general framework of the interactions between chlorine, ammonia nitrogen and the organic compounds which are frequently found in surface water chlorination, the study allowed us to show that the chlorination of highly reactive precursors (such as metapolyhydroxybenzenes and metachlorophenols) can lead to the production of important amounts of chloroform before reaching breakpoint. These results compared to the values of the velocities of the various reactions between chlorine and the ammoniacal compounds.     

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.     

Effects of mixing velocity on anaerobic fixed film reactors

Four laboratory-model upflow anaerobic fixed film reactors (AFFR 1, 2, 3 and 4) treating landfill leachate were subject to identical volumetric organic load (7 kg COD m⁻³ d⁻¹) and hydraulic retention time (3d), but the contents in each unit were continuously recirculated for 10 months at four different velocities, respectively, of 21, 66, 680 and 3063 cm h⁻¹. The objective was to assess the effects of such mixing velocities (ν) on COD removal efficiencies (E), mean cell residence time (MCRT) and substrate utilization rate (U expressed as g COD removed d⁻¹ g⁻¹ VSS). The results showed that the relationships between E and ν and MCRT and ν were inverted U-shaped curves. The two middle reactors (AFFR 2 and 3) had near-optimum velocities (ν₂ and ν₃) with maximum E values of 88–89%. AFFR 4 had a high value of ν scouring biofilm on the biorings, resulting in higher concentrations of SS, VSS and COD in the effluent. All four reactors had nearly similar values of U (1.85–2.14 g COD d⁻¹ g⁻¹ VSS). The value of ν₁ (AFFR 1) was too low to enhance performance and ν₄ was too high to retain the biomass. The optimum recycle velocity, under the test conditions, was in the range of 66–680 cm h⁻¹.     

Photodecomposition du bioxyde de chlore et des ions chlorite par irradiation u.v. en milieu aqueux-partie II. Etude cinetique

The decomposition of ClO₂ and ClO₂⁻ by u.v. radiation leads to the production of chlorate, chloride and oxygen as end-products via complex reactions which are initiated by the products generated by the primary reactions of photolysis (Buxton and Subhani, 1972a; Mialocq et al., 1973; Karpel Vel Leitner et al., 1992). As far as the rate of decomposition is concerned, Bowen and Cheung (1932) and Zika et al. (1985) have shown that the quantum yield of photodecomposition of chlorine dioxide (overall reaction) increases when the wavelength decreases [Zika et al. (1985): φ = 0.46 at 366 nm and 1.4 at 296.7 nm]. However, the values of the quantum yield of photodecomposition of ClO₂ and ClO₂⁻ at 253.7 nm as well as the quantum yields for the primary reactions of photolysis of ClO₂ and ClO₂⁻ at different wavelengths are not given in the literature.The aim of this work was to study the kinetics of photodecomposition of chlorine dioxide and of chlorite by u.v. irradiation.     

Detoxification of seawater used for gas scrubbing in the steel industry

Cyanide ion present in seawater after scrubbing blast furnace and coke ovens gases can be removed by sedimentation of hexacyanoferrate complexes followed by oxidation of residual cyanide with Caro's acid. Zinc ion is removed at the same time by adsorption on the hexacyanoferrate/hydrous ferric oxide precipitate.Sulphide is precipitated as ferrous sulphide, then oxidised by atmospheric oxygen. At 25°C and using an Fe/CN ratio of 1·00, initial concentrations of 50 mg l⁻¹ of CN⁻ and 10 mg l⁻¹ of Zn²⁺ in seawater are reduced to 5–7 mg l⁻¹ and 0·1 mg l⁻¹. Subsequent treatment with H₂SO₅/CN = 1·2 reduces the [CN⁻] to 0·1 mg l⁻¹.Treatment of a combined blast furnace/coke ovens effluent ([CN⁻] = 24 mgl⁻¹, [Zn²⁺] = 4·0 mgl⁻¹) with Fe/CN = 1·5 reduced [CN⁻] to 0·2 mg l⁻¹ and [Zn²⁺] to <0·1 mgl⁻¹. Subsequent treatment with H₂SO₅/CN = 2·0 reduced [CN⁻] to 0·2 mg l⁻¹. The process operates best in the pH range 7–9 and so is not affected by the buffer characteristics of seawater.     

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.     

Influence sur la survie jusqu'a eclosion des embryons de carpe commune (cyprinus carpio l.) apres traitement, pendant la fecondation et le developpement precoce, par le carbendazime, un fongicide antimitotique de synthese

The toxicity of the systemic antimitotic fungicide carbendazim, a benzimidazol compound, was studied both by trout and common carp insemination, as well as on the early development of the common carp.The toxicity is several grades of magnitude higher for these stages of the vital cycle compared with the effect on the adult stages: whereas The Pesticide Manual states that for the adult Carp, an LC₁₀₀ (24 h) > 1000 mg 1⁻¹ we find, during insemination at pH 9: LC₁₀₀ (30 min) < 5 mg l⁻¹ and during insemination at pH 7: LC₁₀₀ (30 min) <2.5 min l⁻¹.During early development we find, for instance, LC₁₀₀ (30 min) < 5 mg 1⁻¹ before the end of activation and LC₁₀₀ (24 h) < 1 mg l⁻¹ before the end of epiboly.In the course of insemination, the egg is more sensitive to carbendazim at pH 7 than at pH 9: this difference may be attributed to a greater solubility of the non ionic form of the molecule in the biological membranes.The resistance of the embryo to short treatment grows at the end of activation. This may be attributed to the decrease of the shell permeability during activation.Before the end of activation, the resistance to short intoxication seems to be able to fluctuate, which perhaps corresponds to the existence of sensitive stages in the mitotic cycle.The resistance to an over 24-h exposure increases abruptly at the end of epiboly, which could correspond to a protective part played by the enveloping layer.We suggest the possibility of classifying aquatic pollutants by correlating their physiological mode of action to the resistance profile of the fish embryo.The carp egg seems to be a favourable biological model for studying the effects of aquatic pollutants.     

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.     

Palm oil refinery wastes treatment

Effluent from the refining of crude palm oil was subjected to physical-chemical and biological treatment. An inclined corrugated parallel plates oil separator spaced at 25 mm was used with hydraulic loading rates of 0.2, 0.5 and 1 m³ m⁻²-h. 91% oil and grease removal could be achieved at 0.2 m³ m⁻²-h. Coagulation and flocculation carried out on batch samples after oil and grease separation revealed that with 100 mg l⁻¹ alum addition BOD was reduced from 3500 to 450 mg l⁻¹ and COD from 8600 to 750 mg l⁻¹ after 30 min settling. Higher doses of alum and doses of polyelectrolyte, activated carbon and sodium hypochloride did not yield significant additional reductions in BOD and COD. Batch dissolved air flotation (DAF) removed 90% of the suspended solids with 2.7% solids in the thickened sludge at an A/S ratio of 0.014. This method yielded the similar effluent quality as the inclined corrugated plates oil and grease separator. Field data from a DAF plant compare closely with data achieved in this study. Activated sludge treatment on the effluent from the oil separator yielded a BOD of 46 mg l⁻¹ with a loading rate of 0.3 g BOD (g MLVSS)⁻¹-day. Total dissolved solids (TDS) remained high and removal through coagulation and chemical oxidation brought the COD level down to around 180 mg l⁻¹. Biokinetic coefficients Y, k_dK and K₃ were found to be 0.85 g VSS (g BOD)⁻¹, 0.016 day⁻¹, 0.12 g BOD (g VSS)⁻¹-day and 510 mg l⁻¹ BOD respectively.     

Enhancement of Nitrobacter activity by heterotrophic bacteria

The present work shows that a supply which is not sterile and which contains organic matter does not interfere with the performance of a column filled with a support previously inoculated with Nitrobacter winogradskyi serotype agilis.Measurements of oxidation rates give results higher than those obtained under axenic conditions (maximum oxidation rate: 220 mg NO₂⁻ h⁻¹ l⁻¹ of reactor volume under non-sterile conditions: 160 mg NO₂⁻ h⁻¹ l⁻¹ of reactor volume under axenic conditions).This finding has concentrated our work on the effect of heterotrophic bacteria and of organic matter on the growth of Nitrobacter. We show that a fermentation filtrate of a heterotrophic bacterium (Pseudomonas sp.) added to a fermenter culture of Nitrobacter produces an increase of activity. Experimental results indicate an appreciable reduction in the latence period (15-0 h) and a considerable increase in the rate of growth of Nitrobacter. (Maximum growth rate with 10% of heterotrophic filtrate: 0.044 h⁻¹; without filtrate: 0.032 h⁻¹.)