Complexation of copper in the effluent of a sewage treatment plant and an estimate of its influence on toxicity to coho salmon

Measurements by cupric ion electrode of the complexing capacity of the effluent from a sewage treatment plant (STPE) averaged 0.300 mg 1⁻¹. Of the complexed Cu 67% was due to compounds of 10,000 MW. Organic compounds removable by activated carbon composed 88% of the total organic carbon and were responsible for 87% of the complexation. Complexation of Cu²⁺ by STPE diminishes the toxicity from total Cu to juvenile coho salmon; the LC₅₀ was 0.164 mg 1⁻¹ for river water vs 0.286 mg 1⁻¹ for 40% STPE. The LC₅₀ of Cu²⁺ was approximately the same (0.017 vs 0.022 mg 1⁻¹) in both matrices; this species thus appears to play a toxic role. The mean survival time in diluted STPE with added Cu was inversely proportional to the Cu²⁺ concentration.     

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.     

Fish toxicity of jet fuels—I. The toxicity of the synthetic fuel JP-9 and its components

The toxicity of the jet fuel JP-9 and its components RJ-4, RJ-5 and MCH was assessed in static bioassays on the warm water fish, golden shiner (Notemigonus chrysoleucas). The 96-h LC₅₀ of emulsions was 2.0 mg 1⁻¹ for JP-9, 0.51 mg 1⁻¹ for RJ-4, 0.61 mg 1⁻¹ for RJ-5 and 72 mg 1⁻¹ for MCH. As determined by the 96-h LC₅₀ values unemulsified fuel (pools of fuel) JP-9 was 235 times less toxic, RJ-4 was 196 times less toxic, RJ-5 was 7700 times less toxic and MCH was 3.3 times less toxic than the corresponding emulsified materials.

In continuous flow bioassays with the water soluble fraction of the fuel and its components the effect on egg hatchability and fry development of flagfish (Jordanella floridae) and rainbow trout (Salmo gairdneri) was studied. The no effect of level on flagfish egg hatchability was 0.23 mg 1⁻¹ for JP-9 and 0.05 mg 1⁻¹ for RJ-5. Concentrations of 0.83 mg 1⁻¹ MCH and 0.2 mg 1⁻¹ RJ-4 did not affect egg hatchability. In rainbow trout studies 97-day LC₅₀ values for RJ-4 and RJ-5 were 0.045 mg 1⁻¹ and 0.072 mg 1⁻¹, respectively, and 23-day LC₅₀ values for JP-9 and MCH were 0.26 mg 1⁻¹ and 1.3 mg 1⁻¹, respectively.

The accumulation of fuels in fish bodies was studied and it was found that flagfish can tolerate a total body burden of 0.5 mg MCH g⁻¹ wet weight without lethality. It was also found that body burdens of 0.43 mg RJ-4 g⁻¹ and of 0.27 mg RJ-5 g⁻¹ on a wet weight basis will produce 50% mortality in rainbow trout.

Voiding of MCH from fish bodies occurs readily in fuel-free water, but RJ-4 and RJ-5 are retained in the tissues.     

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.     

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.     

Sorption of cadmium(II) and zinc(II) ions from aqueous solutions by cassava waste biomass (Manihot sculenta Cranz)

The sorption of two divalent metal ions, Cd(II) and Zn(II), onto untreated and differentially acid-treated cassava waste biomass over a wide range of reaction conditions was studied at 30°C. The metal ion removal from the spent biomass was also measured. The batch experiments show that pH 4.5–5.5 was the best range for the sorption of the metal ions for untreated and acid-treated biomass. Time-dependent experiments for the metal ions showed that for the two metals examined, binding to the cassava waste biomass was rapid and occurred within 30 min and completed within 1 h. High sorption capacities were observed for the two metals. The binding capacity experiments revealed the following amounts of metal ions bound per gram of biomass: 86.68 mg/g Cd, 55.82 mg/g Zn and 647.48 mg/g Cd, 559.74 mg/g Zn for untreated and acid-treated biomass, respectively. It was further found that the rate of sorption was particle-diffusion controlled, and the sorption rate coefficients were determined to be 2.30×10⁻¹ min⁻¹ (Cd²⁺), 4.0×10⁻³ min⁻¹ (Zn²⁺) and 1.09×10⁻¹ min⁻¹ (Cd²⁺), 3.67×10⁻² min⁻¹ (Zn²⁺) for 0.5 and 1.00 M differential acid treatment, respectively. Desorption studies showed that acid treatment inhibited effective recovery of metal ions already bound to the biomass as a result of stronger sulfhydryl-metal bonds formed. Less than 25% of both metals were desorbed as concentration of acid treating reagent increases. However, over 60% Cd and 40% Zn were recovered from untreated biomass during the desorption study. The results from these studies indicated that both untreated and acid-treated cassava waste biomass could be employed in the removal of toxic and valuable metals from industrial effluents.     

Histological and toxicological responses of the mummichog, Fundulus Heteroclitus (L.) to combinations of levels of cadmium and dissolved oxygen in a freshwater

Impact of dissolved oxygen concentration (D.O.) on toxicity of cadmium to mummichogs in a freshwater medium and histological changes associated with exposure were determined. Levels of mortality were related to duration of exposure, cadmium concentration, and levels of dissolved oxygen. Median tolerance concentrations, at 96h, ranged upward from 1.3 to about 3.0 mg Cd 1⁻¹ at 2.3 and 8.5 mg DO 1⁻¹, respectively. Statistical analyses of mortality data showed factors examined were interdependent and that Cd × DO and Cd × time interactions were significant (P < 0.01). No histopathology was evident at 3 mg Cd 1⁻¹, although histopathology was evident in gills from fish exposed to 28 mg Cd 1⁻¹ for 6 1/2 h.

Responses of mummichogs to cadmium in freshwater are compared with results of a previous study involving exposure of the species to cadmium in seawater and with responses of freshwater fishes subjected to various heavy metals. Differences and similarities in patterns of response are discussed in terms of water balance.     

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.     

Acclimation to and biodegradation of nitrilotriacetate (NTA) at trace concentrations in natural waters

Acclimation to and biodegradation of nitrilotriacetic acid (NTA), an organic builder used in synthetic laundry detergents as the sodium salt, was studied at trace concentrations (ppb) in several river waters. The river waters tested ranged from those where extensive NTA exposure via detergents had not occurred, to those where NTA exposure had been continuous for several years. In rivers not previously exposed to NTA, acclimation and degradation were observed at the lowest initial concentration tested, 5 μg 1⁻¹. Degradation of NTA after acclimation followed apparent first order kinetics, and half lives for NTA removal ranged from 7 to 138 h at initial NTA concentrations of 50 and 5 μg 1⁻¹, respectively. Degradation of NTA in water samples where prior NTA exposure had already occurred required no acclimation and was less variable than in unexposed rivers. First order rate constants varied only slightly over a 1000-fold initial concentration range (1–1000 μg 1⁻¹) and NTA half lives ranged from 7 to 17 h. In general, our results indicate that microflora present in natural waters can acclimate to and degrade NTA, even if exposed to only trace levels in laboratory experiments. However, rates of NTA biodegradation are more rapid and less variable in river waters where natural NTA exposure has already occurred.     

Modified amperometric membrane probes for determining free and total residual chlorine in saline cooling waters

Modifications have been made to a Delta Scientific model 82124 free available chlorine probe so that it can be used to determine either the free or the total residual chlorine in cooling waters at coastal and estuarine power stations. For measurements of free residual chlorine, the internal filling solution of the probe was changed for one containing potassium bromide at pH 4. When the sample solution was dosed with potassium bromide and pH 4 buffer, the probe had a linear response over the range 0.04–1.0 μg ml⁻¹ Cl₂ and errors caused by changes in salinity were negligible. Total standard deviations for the analysis of 1.0 and 0.1 μg ml⁻¹ Cl₂ solutions were 0.055 and 0.01 μg ml⁻¹ Cl₂ respectively. For measurements of total residual chlorine a potassium iodide solution at pH 4 was used as the probe's internal filling solution and the sample solution was dosed with potassium iodide and pH 4 buffer. The probe had a linear response over the range 0.02-0.5 μg ml⁻¹ Cl₂, with total standard deviations of 0.05 and 0.01 μg ml⁻¹ Cl₂ at concentrations of 0.5 and 0.1 μg ml⁻¹ Cl₂ respectively.     

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.     

Effect of water hardness on the toxicity of cadmium to micro-organisms

A study was made of the effect of water hardness at different concentrations (viz. 0, 80, 120, 160, 240, 320, 400 and 480 mg l⁻¹ as CaCO₃) on the toxicity of cadmium metal (5 mg 1⁻¹) as sulphate to saprophytic and nitrifying bacteria, with respect to the rate constant (K) and ultimate biochemical oxygen demand (L) which were calculated from BOD data (15 days) using the Thomas Graphical Method. Glucose was used as a source of carbon for micro-organisms. It was observed that the toxicity of cadmium to micro-organisms (both saprophytic and nitrifying) decreased with increasing hardness and reached a maximum at 320 mg 1⁻¹ as CaCO₃ for nitrifying and 400 mg l⁻¹ as CaCO₃ for saprophytic bacteria. After these hardness levels, the ultimate BOD (L) and rate constant (K) showed a decrease. Nitrifying bacteria were found to be more sensitive to the metal as well as to its complexation with calcium or with other ions as they retained their normal activity at a lower hardness level as compared to saprophytic bacteria.     

Hypolimnetic aeration and dissolved gas concentrations: Enclosure experiments

Two large circular enclosures, each containing approx. 550 m³ of water, 14 m deep, and open to the mud-water interface, were used to monitor the effects of hypolimnetic aeration. One enclosure was held as a control, the other aerated every 3 or 4 days for a period long enough (usually < 2 h) to maintain hypolimnetic O₂ levels at > 4 mg 1⁻¹. Nutrient additions (10 g of 90% H₃ PO₄ and 250 g NaNO₃ per week) to each enclosure were controlled from the commencement of the experiment (17 June 1980) until its completion (2 November 1981). Temperatures in both enclosures were identical. Hypolimnetic O₂ levels in the control fell to zero during both summers, but remained at > 4 mg 1⁻¹ in the aerated enclosure. Free N₂ concentrations in the hypolimnion of the aerated enclosure was higher than in the control. Concentrations of H₂S in the control hypolimnion increased to > 5 mg 1⁻¹ and concentrations of CH₄ increased to > 18 mg 1⁻¹. Both remained at or near zero in the aerated enclosure. Tests of aerator efficiency suggested that the full air-lift design that was employed had an average O₂ exchange efficiency of 42% which is higher than the values reported for most other designs.     

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.     

Growth of Selenastrum capricornutum in natural waters augmented with detergent products in wastewaters

A determination of whether the removal of phosphate builders from detergents would modify the ability of domestic secondary treated sewage effluent to stimulate the growth of a test alga (Selenastrum capricornutum-Printz) in receiving waters alone and augmented with detergent products was made. The lakes used as sources of test waters were located in northeastern New York State and possessed total phosphorus concentrations ranging from ca. 0.01 to 0.04 mg P1⁻¹.

The alga experienced stimulation in all three test lake waters from secondary sewage containing detergent with phosphate or detergent without phosphate. A concentration of 60 μg P 1⁻¹ was sufficient to effect significant algal growth in two of the test waters; however, concentrations ranging up to 110 μg P 1⁻¹ did not generate such a response in the third test water. This latter result and others suggested that neither phosphorus nor other nutrients from these wastewater additions were the factors fully accountable for the observed response(s).     

Adsorption of trace metals on aluminium oxide: A simulation of processes in freshwater systems by close approximation to natural conditions

The interaction of the trace metals Cu, Co, Zn, Ni, Pb and Cd with aluminium hydroxide precipitated in-situ from homogeneous solution was studied. Using total concentrations of 10⁻⁴ M Al, 10⁻⁷ M Zn, Cu, Co, Ni and 10⁻⁸ M Pb and Cd a removal of Zn, Cu, Pb, Cd from solution occurred together with Al, while Co and Ni concentrations in solution remained unchanged. The binding of Cu, Pb and Zn, Cd is in agreement with the effect predicted by using published (resp. evaluated for Zn and Cd), values for stability constants of surface complexes on preformed Al₂O₃-suspension. The different behaviour of these elements and of Co and Ni is expected from the hydrolysis and adsorption tendencies. The experimental conditions correspond to natural conditions in lake waters, where due to the pH-dependent solubility of aluminium hydroxide, in-situ precipitation may occur and cause the scavenging of trace elements.     

Microbial uptake of cadmium and its effects on the biochemical oxygen demand at various temperatures

Uptake of cadmium by microbes at different temperatures has been studied at pH 7. Glycine was used as a source of carbon for microorganisms in the BOD bottle at 20, 30, 40 and 50°C with varying concentrations of cadmium: control 0.0437, 0.437, 0.875 and 1.31 mg 1⁻¹ in each set. The influence of temperatures on the toxic effects of cadmium has been studied with respect to rate constant (k) and ultimate biochemical oxygen demand which were calculated from BOD data using Thomas Graphical method. Consumed cadmium mg 1⁻¹ was determined after eight days and it varied from 14.04 to 32.40% at four temperatures. Highest consumption of Cd was noted in the set at 30 and 40°C and lowest at 50°C.     

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 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.     

Automated fluorometric method for determination of boron in waters, detergents and sewage effluents

An automated method for the determination of boron in natural waters, detergents and sewage effluents is described. The method is based on the reaction of 4'-chloro-2-hydroxy-4-methoxybenzophenone (CHMB) with boron to produce fluorescent species, in a 90% sulfuric acid medium. The method has been made specific to remove any interferences from all major and minor ions and other organic compounds normally present in water. The method is capable of measuring different chemical forms of boron such as boric acid, borax, sodium perborate and tetraphenyl boron. The method analyses 10 samples per hour, in the 5–100 μg 1⁻¹ boron range. The rate of sample analysis can be increased to 20 per hour at higher concentration ranges. The limit of detection is 1 μg 1⁻¹ boron.