Formation equation of halogenated organic compounds when water is chlorinated

Various halogenated organic compounds are formed by chlorination of water. In this study, formation of organic compounds halogenated from a reagent humic acid and extract of a leaf mold were examined under various conditions. The following overall formation equation was obtained from empirical data under the practical wide range when free chlorine remained.

[TOX]=k_TOX[TOC][Cl₂]_ot^β.

Here, [TOX] is the concentration of total organic halogen after t h in units of mg chlorine per liter; [TOC] and [Cl₂]_o are concentrations of total organic carbon and dosed chlorine in units of mg per liter; k_TOX is the rate constant and and β are parameters. From the values of k_TOX, and β, the character of organic substances i.e. precursor of halogenated organic compounds, in water can be evaluated. The values k_TOX, and β for humic acid are 0.053, 0.28 and 0.13, and the values for extract of the leaf mold are 0.032, 0.36 and 0.15, respectively. The activation energies are 10 kJ mol⁻¹ and 11 kJ mol⁻¹ for the reactions of humic acid and leaf mold extract, respectively.     

Photodecomposition du bioxyde de chlore et des ions chlorite par irradiation U.V. en milieu aqueux—partie I. Sous-produits de reactionPhotodecomposition of chlorine dioxide and chlorite by U.V.-Irradiation—Part I. Photo-products

Literature data about the photochemistry of oxychlorine compounds in aqueous solutions (flash photolysis, pulse radiolysis, solar radiation) indicate that the products (ClO, Cl, O, O⁻,…) generated from the primary photochemical reactions of decomposition of chlorine dioxide and hypochlorite can then initiate complex reactions which lead to the formation of many secondary products (Cl₂O₂, Cl₂O₁, ClO⁻,…) and of chlorate, chloride and molecular oxygen as end-products (Table 1). The aim of this work was to study the photodecomposition of aqueous solutions of chlorine dioxide and chlorite in u.v. reactors equipped with low pressure mercury vapour lamps in order to show the effects of pH and of the initial concentrations on the nature of photoproducts and on the rate of photodecomposition of ClO₂ and ClO₂⁻. This paper presents the data obtained for the identification of photoproducts. The kinetics of photodecomposition will be presented in another paper (Part II).     

Empirical rate equation for trihalomethane formation with chlorination of humic substances in water

Trihalomethane (THM) in drinking water is formed by chlorination of humic substances. In this study, the rates of THM formation in aqueous solution of humic acid were examined under various conditions. The following rate equation was obtained empirically. [THM] = k (pH − a)[TOC][Cl₂]₀^mtⁿ.

Here, [THM] is the concentration of total THM after t h, [TOC] and [Cl₂]₀ are the concentrations of total organic carbon and chlorine dose, k is the rate constant and a, m and n are parameters. The values of k, a, m and n for humic acid as reagent were obtained as 8.2 × 10⁻⁴ (l^mmg^−mh⁻ⁿ), 2.8, 0.25 and 0.36, respectively. The activation energy was obtained as 37 kJ mol⁻¹. Further, it was proved that the above equation could be applied to the rates of THM formation from precursors in actual river and lake waters.     

Removal of saxitoxins from drinking water by granular activated carbon, ozone and hydrogen peroxide--implications for compliance with the Australian drinking water guidelines

In a laboratory-scale trial, we studied the removal of saxitoxins from water by ozone, granular activated carbon (GAC) and H₂O₂, and considered the implications of residual toxicity for compliance with the Australian drinking water standards. Cell-free extracts of Anabaena circinalis were added to raw, untreated drinking water obtained from a water supply reservoir to provide a toxicity of 30 μg (STX equivalents) l⁻¹. Ozone alone, or in combination with H₂O₂, failed to destroy the highly toxic STX and GTX-2/3, and only partially destroyed dc-STX, and the low-toxicity C-toxins and GTX-5. In all cases, the toxicity of the water was reduced by less than 10%. GAC removed all of the STX, dc-STX and GTXs, but only partially removed the C-toxins. However, the residual toxicity was reduced to the suggested Australian drinking water guideline concentration of 3 μg (STX equivalents) l⁻¹ without O₃ pre-treatment. Modelling the spontaneous chemical degradation of residual C-toxins following treatment shows that residual toxicity could increase to 10 μg l⁻¹ after 11 d due to formation of dc-GTXs and would then gradually decay. In all, residual toxicity would exceed the Australian drinking water guideline concentration for a total of 50 d.     

A bench study on lead removal from battery manufacturing wastewater by carbonate precipitation

A residual soluble Pb ≤ 0.2 mg/l has been measured after hydrocerussite precipitation in the range of pH 9–10 and filtration with 0.45 μm filter, at a total carbonate concentration (C_T) of about 1.5 × 10⁻⁴ M. Filterability and sedimentation were optimized by minimizing the “relative supersaturation” coefficient during precipitation. Pb abatement was implemented in the pH range 9–9.5, following a preliminary precipitation step consisting of a slow, gradual change of pH from 6.8 to 7.8 with 0.1 M NaOH solution. The crystals formed may settle within 24 h, allowing Pb to be recovered as Pb₃(CO₃)₂(OH)₂.     

Chlorine dioxide disinfection of drinking water—An evaluation of a treatment plant

A treatment plant for lake Kinneret water, comprising treatment by two filtration steps, flocculation and disinfection with chlorine dioxide, was studied with a view to evaluating the effect of ClO₂ disinfection on drinking water quality and determining the optimal mode of operation for the treatment plant. Four modes of operation were studied and the optimal mode was defined as that in which the flocculant (aluminium sulphate) was introduced before the first, and ClO₂ after the second, filtration.

The finished water contained a residue of approx. 0.2 mgl⁻¹ ClO₂, approx. 0.35 mgl⁻¹ ClO₂⁻ and low concentrations of suspended matter (1.5 mgl⁻¹) and of chlorophyll (0.1 μgl⁻¹). Trihalomethane concentrations were negligible, and the bacteriological quality of the water was within the health authorities' requirements. It was shown that disinfection of treated water (after flocculation and filtration) was much more effective than that of raw water. Furthermore, disinfection in the optimal mode prevents accumulation of high chlorite concentrations leaving a residue of ClO₂.     

Factors influencing oxygen transfer in fine pore diffused aeration

A bench-scale experiment was conducted in a 701. tank of tap water to examine the effect of four design variables on oxygen transfer in a fine pore diffused aeration system. The experiment used non-steady state gas transfer methodology to examine the effect of air flow rate, air flow rate per diffuser, orifice diameter and reduced tank surface area on the overall oxygen transfer coefficient (K_La₂₀, h⁻¹); standard oxygen transfer rate (OT₂, g O₂ h⁻¹); energy efficiency (E_p, g O₂ kWh⁻¹) and oxygen transfer efficiency (E_o, %). The experiments demonstrated that K_La₂₀ and OT_s increased with air flow rate (9.4–18.8 1 min⁻¹) in the 40 and 140 μ diameter orifice range; however, E_p and E₀ were not affected. Reducing the air flow rate per fine pore diffuser (40 and 140 μ diameter pore size) significantly increased K_La₂₀, OT_s, E_p and E₀. A decrease in orifice diameter from 140 to 40 μ had no effect on K_La₂₀, OT_s, E_p and E₀. A reduction in tank surface area had a marginally significant inverse effect on K_La₂₀ and OT_s, and no effect on E_p and E_o. The mean bubble size produced by the 40 and 140 μ diffusers was 4.0 and 4.2 mm, respectively. There was no consistent effect of air flow rate on bubble size within the range of air flow rates used in this experiment. In clean water aeration applications, the optimum system efficiency will be obtained using the largest number of fine pore diffusers operated at low air flow rates per diffuser. In wastewater treatment plants, higher air flow rates per diffuser should be used to prevent diffuser biofouling and keep biological solids in suspension. Wastewater systems are purposely operated at less than optimum transfer efficiencies in exchange for reduced diffuser maintenance and improved mixing. In either situation, changes in tank surface area and diffuser pore size (provided that pore diameter remains between 40 and 140 μ) are unlikely to have any significant effect on aeration system efficiency.     

Effect of exposure time and copper concentration on reproduction of the fathead minnow (Pimephales Promelas)

Three concurrent studies were conducted to determine the chronic effect of prespawning exposure to various concentrations of copper on fathead minnow reproduction. Copper was introduced into the three exposure systems to give 6-, 3-, and 0-months exposure prior to spawning. Prespawning exposure time had no significant effect on reproduction. Number of eggs produced per female decreased, however, with increase in copper concentrations. Egg production at copper concentrations of 37μg 1⁻¹ and higher was significantly lower (P = 0.05) than in the control, but at concentrations of 24μg 1⁻¹ and lower it was not different. The maximum acceptable toxicant concentration (MATC) was estimated to be 32μg Cu 1⁻¹, which is 0.07 of the 96h LC₅₀. This application factor for copper is similar to those found in other studies.     

Toxicities of total and chelex-labile cadmium to salmon in solutions of natural water and diluted sewage with potentially different cadmium complexing capacities

The LC₅₀ for total Cd averaged 4.8 and 8.0 μg1⁻¹ in river water and 33% sewage-treatment-plant effluent (STPE), respectively, and for Chelex-labile Cd, 3.9 and 5.6 μg1⁻¹, respectively. The LC₅₀ values for total Cd were significantly (P < 0.05) different, indicating a reduction in toxicity of Cd in the presence of 33% STPE, presumably due to complexation of Cd²⁺. The similarity of LC₅₀ values for Chelex-labile Cd indicates that that fraction contained toxic species of Cd at approximately the same concentration(s) in both river water and 33% STPE; it is therefore considered a better measure of Cd toxicity than total Cd. Furthermore, mortality was correlated with the concentration of Chelex-labile Cd but not with that of Chelex-nonlabile Cd. Measurements of Cd²⁺-complexing capacity by the Chelex method indicated that toxicity was due, at least in part, to Cd²⁺. Values were less than those obtained by the ion-selective-electrode method; these indicated that toxicity was due only to complexed Cd. Values from both methods were uncorrelated with LC₅₀ values.     

Toxicity of chlorine to juvenile spot, Leiostomus Xanthurus

The sensitivity of juvenile spot, Leiostomus xanthurus, to total residual chlorine (TRC) in flowing sea-water was investigated. Incipient LC₅₀ bioassays, histopathology, avoidance tests and the combined effect of thermal stress and TRC were used to assess sensitivity.

Estimated incipient LC₅₀ values were 0.12 mg 1⁻¹ TRC at 10°C and 0.06 mg 1⁻¹ TRC at 15°C. Histological examination of spot used in the incipient LC₅₀ bioassay at 15°C and sacrificed while alive indicated pseudobranch and gill damage occurred in individuals exposed to a measured TRC concentration of 1.57 mg 1⁻¹. Spot exposed to lower concentrations of TRC, 0.02 0.06 mg 1⁻¹ at 15°C and sacrificed alive showed no consistent tissue damage.

Spot demonstrated temperature dependent avoidance responses to TRC. At 10°C, a concentration of 0.18 mg 1⁻¹ was required for significant (X²; P < 0.05) avoidance; at 15 and 20°C, spot showed significant avoidance of TRC concentrations as low as 0.05 mg 1⁻¹.

Simultaneous exposure of spot to thermal stress (5, 10 or 13°C above the acclimation temperature of 15°C) at measured TRC concentrations of 0.05 0.07 and 0.34–0.52 mg 1⁻¹ demonstrated a significant, (Z²) with Yates correction, P < 0.05) increase in sensitivity to TRC with increased temperature and exposure times for some of the groups tested.     

Simultaneous determination of trace amounts of free cyanide and thiocyanate by a stopped-flow spectrophotometric method

Simultaneous determination of free cyanide and thiocyanate was investigated using a stopped-flow spectrophotometric method. 1,3-dimethylbarbituric acid/isonicotinic acid at pH 5.2 was used as the colour reagent for both cyanide and thiocyanate determinations. The absorption spectrum of the complex formed by cyanide and thiocyanate with the colour reagent has a maximum wavelength at 600 nm, giving a low detection limit of 0.5 μg l⁻¹ for cyanide and 1.5 μg l⁻¹ for thiocyanate. Two proposed processes — 1,3-dimethylbarbituric acid combined with formaldehyde masking cyanide and the ferric-thiocyanate methods — can simultaneously determine free and other simple forms of cyanide and thiocyanate existing at pH 5.2; comparison of results demonstrates that both approaches are in agreement. By taking into account the effect of temperature on colour development and by using the ratio of the regression slopes, one kind of standard solution (thiocyanate) can be used for both cyanide and thiocyanate calibration, thereby avoiding the need to use toxic cyanide standard solutions.     

Effect of electrolyte composition, and of added iron(III) in the presence of selected organic complexing agents, on nickel(II) precipitation by lime

The effect of effluent composition involving the common anionic species Cl⁻, SO₄²⁻ and CO₃²⁻ on the efficiency of nickel(II) precipitation, modelling lime (CaO) as the precipitant, has been investigated using the solubility domain approach. Solubility domains were based on the phases that were found to limit metal solubility for systems representing potential effluent composition limits. These phases were found to resemble their mineralized counterparts, but with a lower degree of structural order. At higher SO₄²⁻ and CO₃²⁻ concentrations both gypsum (CaSO₄·2H₂O) and calcite (CaCO₃) were formed, but these had little effect on the observed residual nickel solubility. The calculated solubility domains were found to generally encompass the experimentally determined solubilities, thereby providing quality assurance ranges for hydroxide precipitation. The effect of the complexing anions tartrate and EDTA⁴⁻ on residual Ni(II) in solution as well as the effects of the addition of Fe(III) on the removal of Ni(II) complexed by these species are described.     

Ammonia oxidation in nitrosomonas at NH3 concentrations near km: Effects of pH and temperature

Nitrosomonas europaea from continuous pure cultures was incubated with 26.4 μ M NH₃(= 0.37 mg NH₃-N l⁻¹) at various NH₄⁺ concentrations, pH values and temperatures. Measured rates of nitrite formation were significantly influenced by pH. Likewise unexpectedly, the maximum ammonia oxidation rate occurred between pH 6.7 and 7.0. Temperature had an even stronger effect on the rate of ammonia oxidation than the availability of NH₃. It is concluded that the assumption of a strict dependence of the rate of ammonia oxidation on substrate concentration is an unjustified oversimplification. Among the mechanisms which could explain ammonium uptake and oxidation near or below pH 7.0, the formation of NO from HNO₂ is considered.     

Some problems in the determination of total residual “chlorine” in chlorinated sea-water

In the determination of residual chlorine in sea-water by the amperometric titrimetric method, potassium iodide must be added to the sample before the addition of the pH 4 buffer, and the addition of these two reagents should not be more than one minute apart. Serious analytical error may arise if the order of the addition of the reagents is reversed. There is no evidence suggesting the formation of iodate by the reaction between hypobromite and iodide. For concentrations of residual chlorine below one mg 1⁻¹, iodate, which occurs naturally in sea-water, may cause serious analytical uncertainties. In sea-water, the preferred concentration unit of residual chlorine is μM. The unit, mg 1⁻¹, must be used with care and clear definition. The unit, ppm, should be avoided.     

Measuring maximum specific growth rate and half saturation coefficient for activated sludge systems using a freeze concentration technique

To measure the maximum specific growth rate (μ_max) and the half saturation coefficient (K_s), a simple respirometric technique was used, where differing volumes of concentrated wastewater were contacted with biomass in a respirometer and the response measured as a change in oxygen uptake rate (ΔOUR). The ΔOUR was then related to the growth rate, and a series of substrate concentration/growth rate relationships determined from which μ_max and K_s were calculated. A freeze concentration technique was developed to concentrate the wastewater. The concentration technique did not alter the response of the microorganisms to the wastewater. Maximum specific growth rates (μ_max) and half saturation coefficients (K_s) were found to vary between 1.3 and 1.9 d⁻¹ and 1.5 and 3.2 mg l⁻¹, respectively.     

Removal of As(III) and As(V) from water using a natural Fe and Mn enriched sample

The arsenic removal capacity of a natural oxide sample consisting basically of Mn-minerals (birnessite, cryptomelane, todorokite), and Fe-oxides (goethite, hematite), collected in the Iron Quadrangle mineral province in Minas Gerais, Brazil, has been investigated. As-spiked tap water and an As-rich mining effluent with As-concentrations from 100 μg L⁻¹ to 100 mg L⁻¹ were used for the experiments. Sorbent fractions of different particle sizes (<38 μm to 0.5 mm), including spherical material (diameter 2 mm), have been used. Batch and column experiments (pH values of 3.0, 5.5, and 8.5 for batch, and about pH 7.0 for column) demonstrated the high adsorption capacity of the material, with the sorption of As(III) being higher than that of As(V). At pH 3.0, the maximum uptake for As(V) and for As(III)-treated materials were 8.5 and 14.7 mg g⁻¹, respectively. The Mn-minerals promoted the oxidation of As(III) to As(V), for both sorbed and dissolved As-species. Column experiments with the cFeMn-c sample for an initial As-concentration of 100 μg L⁻¹ demonstrated a very efficient elimination of As(III), since the drinking water limit of 10 μg L⁻¹ was exceeded only after 7400 BV total throughput. The As-release from the loaded samples was below the limit established by the toxicity characteristic leaching procedure, thus making the spent material suitable for discharge in landfill deposits.     

Mixing effect and combustion efficiency in compartment fires

A new model for compartment fires is proposed in which the new concept of combustion efficiency based on the mixing process of the fuel gas and air has been considered. This new concept was formulated by the mixing parameter, μ. It was defined as μ1 − exp(−τ^*) and τ^* was related to the residence time t_R and mixing time t_M, that is, τ^* = t_R/t_M.

A simple one zone model was used in order to demonstrate the effect of the mixing process. Theoretical results were in good agreement with the experimental results of methanol and PMMA compartment fires, and especially the scale effect of the compartment was predicted successfully. Further, the similarity law for this scale effect was investigated, and the upper and lower limits of flashover were defined using a new number F. This F number was found to be the key parameter for the prediction of the compartment fire behavior.     

Variation of ATP content in Scenedesmus dimorphus cells grown in a chemostat culture and its comparison with chlorophyll-A content

The variations of ATP and chl-a contents in Scenedesmus dimorphus cells grown in a chemostat culture under nutrient limitation were investigated. ATP and chl-a contents per algal dry weight varied in the ranges of 0.15–1.64 μg mg⁻¹ (0.33–3.82 μg mg⁻¹ as ATP/C ratio) and 0.32–1.32% (7.8–30.8 μg mg⁻¹ as chl-a/C ratio), respectively, under the conditions of T-N/T-P ratio of 2–50 by weight and dilution rate of 1–4 per day. At every T-N/T-P ratio, both ATP and chl-a contents increased as dilution rate increased. At a given dilution rate, ATP content decreased systematically as T-N/T-P ratio increased, with the only exception at dilution rate of 4 per day. It was considered based on the result that ATP or chl-a can hardly be used successfully as an indicator of algal biomass.     

Removal of cadmium and manganese by a non-toxic strain of the freshwater cyanobacterium Gloeothece magna.

The ability of both living and dry cells of Gloeothece magna, a non-toxic freshwater cyanobacterium, to adsorb cadmium and manganese is demonstrated in this study. Chlorophyll a content of living cells was not influenced by either cadmium or manganese concentrations, indicating that adsorption of both Cd²⁺ and Mn²⁺ by living cells of G. magna, was independent of the metabolic state of the organism. Moreover, the adsorption of both Cd²⁺ and Mn²⁺ to living cells and dry cells, was dependent on the metal concentrations, and fitted the Freundlich adsorption isotherm. However, dry cells had larger binding capacity for both Cd²⁺ (K_f=912.6) and Mn²⁺ (K_f=2398) than living cells (K_f=151.4 & 63, respectively). The role of the capsular polysaccharides, the main constituents of the cyanobacterial envelope, in binding these two metals was also studied. Polysaccharide extracts of this organism adsorbed high amounts of both Cd²⁺ (115–425 μg mg⁻¹) and Mn²⁺ (473–906 μg mg⁻¹). This study suggests that G. magna would probably be cultured in water bodies contaminated by heavy metals to ameliorate their toxicity. Also dry material of this cyanobacterium being a non-toxic species, could be used as a safe biofilter to remove toxic metals from drinking water.     

Utilisation de l''algue oocystis sp. pour le traitement tertiaire des eaux usées—I. Culture en vrac de cellules préalablement conditionnées en cyclostat

With the aim of developing an efficient and economic method for the tertiary treatment of wastewater, a two-phased culture system of Oocystis alga is presented. During the first phase, a unialgal strain grows in a cyclostat supplied with secondary effluents diluted to a low concentration (50 μM NH₄⁺, i.e. 0.7 mg N 1⁻¹) of inorganic ions. Once the equilibrium is reached (i.e. the cell population is conditioned and the nutrient concentration is zero), in a second phase, the starved cells are mixed with a secondary effluent which has a higher nutrient content (200–400 μM NH₄⁺, i.e., 2.8–5.6 mg N 1⁻¹). Ion depletion (NH₄⁺, NO₃^-, NO₂^- and PO₄^3-) follows specific kinetics; successive identifiable stages related to photoperiod lead to a complete stripping of nutrients. In addition to ion concentrations, pH and cell population were determined every 2 h during the experiment. Results and conclusions are presented.