The acute toxicity of vanadium and copper to eyed eggs of rainbow trout (Salmo gairdneri)

The effects of vanadium (25–595 mg l⁻¹) and of copper (0.03–4.78 mg l⁻¹) on embryonic survival and hatching of eyed eggs of rainbow trout, Salmo gairdneri, were investigated. Copper was approx. 300-fold more toxic than vanadium (96-h LC₅₀ = 0.4 and 118 mg l⁻¹, respectively) but had little effect on the timing of hatch. Vanadium induced premature hatching of eyed eggs at concentrations from 44 to 595 mg l⁻¹. Concentrations of copper required to produce lethality in eyed eggs were similar to concentrations required to produce mortality in juveniles. Vanadium concentrations approx. 15 times higher were required to produce mortality in eyed eggs than in juveniles. Therefore, acute exposure of eyed rainbow trout eggs to vanadium is not a sensitive toxicity test for use in establishing water quality criteria or maximum acceptable toxicant concentrations.     

Comparison of chlorine and chlorine dioxide toxicity to fathead minnows and bluegill

The comparative toxicity of total residual chlorine (TRC) and chlorine dioxide (ClO₂) was evaluated by conducting 96 h flow-through bioassays with three types of fish. The fish were subjected to an intermittent exposure regime in which biocide residuals were present for approx. 2-h periods beginning at 0, 24, 48 and 72 h into the tests. These conditions simulated the antifouling procedure (1 h day⁻¹ biocide addition) used to control biofouling of nuclear reactor heat exchangers at the Savannah River Plant near Aiken, South Carolina. LC₅₀ values showed that ClO₂ was approx. 2–4 times more toxic than TRC to: (1) juvenile and 1-year-old fathead minnows (Pimphales promelas); and (2) young-of-the-year bluegill (Lepomis macrochirus).The TRC mean 96-h LC₅₀ values were: 0.08 mg l⁻¹ for juvenile fathead minnows, 0.35 mg l⁻¹ for adult fathead minnows and 0.44 mg l⁻¹ for young-of-the-year bluegills. The ClO₂ mean LC₅₀ values were: 0.02 mg l⁻¹ for juvenile fathead minnows, 0.17 mg l⁻¹ for adult fathead minnows and 0.15 mg l⁻¹ for young-of-the-year bluegills.     

Aluminium complexation by an aquatic humic fraction under acidic conditions

Equilibrium dialysis and acid-base titration were used to investigate the interactions between Al and a fraction of aquatic humic substances (HS), in the pH range 3–5. Binding of Al by the HS increased with Al³⁺ activity and with pH. Under conditions relevant to natural waters, υ (mol Al bound per gHS) varied from 0 to 1.5 × 10⁻³. The data were modelled with an emprical linear logarithmic expression (Model I) and on the basis of the polyelectrolyte nature of the HS, incorporating competitive binding of H⁺ and Al³⁺ (Model II). Both models gave tolerable fits (r = 0.93). Model I is simpler to apply, while Model II allows the calculation of proton release accompanying Al binding, and provides information on the net charge of the Al---HS complexes. The results were used to calculate the distribution of Al between organic and inorganic forms under conditions prevailing in acidic natural waters.     

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.     

The complexation of protons, aluminium and calcium by aquatic humic substances: A model incorporating binding-site heterogeneity and macroionic effects

A model is presented that describes the competitive binding of protons and metal ions (Al³⁺, AlOH²⁺, Ca²⁺) by humic substances (HS) in the pH range 3–6 and at different ionic strengths, and allows the net humic charge to be calculated. The HS are treated in terms of two types of carboxyl group, together with other more weakly-acidic groups, and the influence of humic (macroionic) charge is taken into account. Eight parameters are involved: total humic acidity, which can be measured directly, content of COOH groups, 4 intrinsic equilibrium constants (2 for H⁺ binding, 2 for metal binding), and 2 parameters accounting for charge effects at different ionic strengths. The model was applied to 4 aquatic humic samples, parameters being estimated from acid-base titration data. The equilibrium contents did not vary greatly among the humic samples, which is consistent with the idea that the functional groups in each sample are chemically the same. The effect of humic charge on complexation varies considerably among the samples. The model was reasonably successful at predicting humic-bound Al in laboratory-prepared solutions and field samples. Calculations based on the model suggest that, (1) Ca²⁺ does not compete significantly with Al for binding to HS under natural acid conditions, and (2) that there is a direct relationship between humic solubility and net humic charge.     

Direct analytical procedure for determination of volatile organic acids in raw municipal wastewater

A direct analytical method for identification and determination of the individual volatile acids in raw sewage was developed. The proposed procedure is rapid, omitting tedious sample pretreatment and thus avoiding possible losses involved in steam distillation, evaporation or extraction. It consists of direct injection of raw sewage into a gas chromatograph, including Carbowax 20 M on acid washed Chromosorb W column and a flame ionization detector. Sample preparation is confined to addition of solid metaphosphoric acid to the raw sewage, and removal of precipitated proteins and suspended solids by centrifugation.The direct injection method proved to be practicable, accurate and rapid. Volatile acids content in raw municipal sewage in Haifa, Israel, was found to be in the range of 150–160 mg l⁻¹, of which 120–125 mg l⁻¹ was acetic acid, 30–33 mg l⁻¹ propionic acid, 6–8 mg l⁻¹ butyric acid, 2 mg l⁻¹ isovaleric acid, and 0.5–1 mg l⁻¹ valeric acid.     

Toxicity-, accumulation- and elimination studies of α-hexachlorocyclohexane (α-HCH) with saltwater organisms of different trophic levels

A short-term study with α-HCH was carried out with saltwater organisms of different trophic levels the alga—Dunaliella, the crustacean—Artemia, and the fish—Lebistes, acclimated to water of gradually increased salinity.Within the solubility range of α-HCH in saltwater (1.4 mg l⁻¹) there was no influence on the growth of Dunaliella. The LC50 (4 days) for Artemia was 0.5 mg l⁻¹, the EC50 (2 and 4 days)—E = mortality and immobilization, for Lebistes was 1.4 and 1.3 mg l⁻¹ respectively. In the longterm study the LC10 (35 days) for Lebistes proved to be 0.5 mg l⁻¹.In the accumulation studies the concentration factor was about 60–90 with Artemia and about 500 with Lebistes; equilibrium levels were reached within 24 and 48 h respectively. In the elimination studies the α-HCH concentration was halved within 48–72 h in Artemia and within 10 h in Lebistes.     

Removal of humic substances from natural waters by reverse osmosis

An investigation of the potential use of reverse osmosis for the removal of humic substances in order to remove colour and haloform precursors in small waterworks has been carried out, using three different laboratory scale reverse osmosis units and several different membranes.Membrane pore size was found to be the most important factor that influenced both the permeate quality and the product water flux. Pressure was found to have no significant influence on permeate quality, but was linearly related to product water flux. The concentration of humic substances in the influent was not found to affect product water flux but the transport of humics across the membrane was found to be dependent upon influent concentration. For the selected membranes, the removal of humic substances amounted to 80–100% in terms of colour removal, and 50–99% in terms of permanganate value reduction. The most suitable membranes for the different available units were found to be Osmonics SEPA 89 (permeate flux 251 m⁻² h⁻¹ at 15 bars), DDS 865 (permeate flux, 1201 m⁻²h⁻¹ at 40 bars) and PCI T2A (permeate flux 901 m⁻²h⁻¹ at 20 bars). At suspended solids concentrations higher than 100 mg 1⁻¹ of bentonite, product water flux was significantly reduced.     

The behaviour of phosphate, nitrate, chloride and hardness in twelve welsh rivers

Selected water quality data from 12 rivers in the area administered by the Welsh Water Authority were analysed for the period 1974–1981. Mean nitrate-nitrogen concentrations varied from 0.4 to 3.7 mg l⁻¹ and were significantly related to the intensity of average catchment run-off; mean orthophosphate-phosphorus concentrations ranged from the limit of analytical detection to 0.730 mg l⁻²; chloride from 11 to 42 mg l⁻¹ and total hardness (as CaCO₃) from 13 to 173 mg l⁻¹. Seasonal patterns of change in concentration were established, generally for all determinands at most sites, but no long-term trends were detected. Relationships between concentration and flow were established for most determinands at many sites, increasing flow generally resulting in decreased concentration. However, positive relationships between nitrate concentration and flow were established at seven sites. Mass flows (kg ha⁻¹ yr⁻¹) were calculated at nine sites only: nitrate-N 4.8–24.6; orthophosphate-P 0.16–3.81; chloride 79–334; total hardness (as CaCO₃) 196–1629. Orthophosphate flows were related to sewered population density, estimates of per capita and land drainage contributions being 1.9 g day⁻¹ and 0.112 kg ha⁻¹ yr⁻¹ respectively.     

The toxicity of chlorine to a common vascular aquatic plant

Myriophyllum spicatum was exposed to various chlorine concentrations on a continuous and intermittent basis in 96-h toxicity studies utilizing a proportional diluter. Continuous exposure to chlorine concentrations as low as 0.05 mg l⁻¹ total residual chlorine (TRC) depressed shoot and total plant dry weights approx. 30% relative to controls. Shoot length was depressed approx. 16% at this concentration. Chlorophyll a was depressed 25% at 0.1 mg l⁻¹ TRC. However, intermittent exposure of plants to chlorine for three 2-h periods daily for 96 h indicated an insensitivity to repeated short term chlorine exposure at all concentrations but 1.0 mg l⁻¹ TRC. These results indicate that high level chlorine discharges from waste water facilities and electric generating plants could be a contributing factor impacting nearby submerged aquatic vegetation.     

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.     

Addition of NaOH, limestone slurry and finegrained limestone to acidified lake water and the effects on smolts of atlantic salmon (Salmo salar L.)

A neutralization experiment comparing NaOH, limestone slurry and finegrained limestone was performed using smolts of Atlantic salmon as testfish. Smolts were raised on chronically acid Lake Liervatn (pH = 4.9–5.4, conductivity = 55 μ S cm⁻¹, Ca = 1.3 mg l⁻¹, labile Al = 40 μg l⁻¹). As a result testfish were sublethally stressed prior to the experiment, as indicated by low levels of plasma chloride. During the experiment, smolts were held in keepnets in the middle of large plastic enclosures without sediment contact. Rapid changes in pH and Al-speciation were recorded after addition of the neutralizing agents. No mortality of fish occurred during the 3 days exposure. Plasma chloride levels in fish exposed to limestone slurry, limestone and the lowest concentration of NaOH (pH = 5.9) did not differ significantly from levels in fish from the reference group. Fish exposed to the highest concentration of NaOH (pH > 7.45), however, experienced a significant decrease in plasma chloride levels. Increased sublethal stress in treatments with NaOH was presumably caused by the presence of aluminate ions [Al(OH)₄⁻] at high pH and by low concentrations of Ca. The importance of maintaining pH below 7 when using bases with monovalent cations is emphasized. Adding inorganic aluminium to the lake water induced loss of plasma chloride within 48 h at 70 μg labile Al l⁻¹ at pH 5.1 and 1.2 mgCa l⁻¹.     

The effect of surfactants on the mixed chelate extraction-atomic absorption spectrophotometric determination of copper, nickel, iron, cobalt, cadmium, zinc and lead

Twelve surfactants representing pure cationic, anionic and non-ionic detergents, three commercial detergents, sodium pyrophosphate, sodium tripolyphosphate, a soap, nitrilotriacetic acid (NTA), EDTA, and humic acid were investigated for their effect on the extraction-atomic absorption spectrophotometric determination of copper, nickel, iron, cobalt, cadmium, zinc and lead. Cations were extracted into 10 ml of a solution containing diphenylthiocarbazone, 8-quinolinol and acetyl acetone in ethyl propionate. To avoid emulsion formation, the maximum concentration of linear alkylate sulphonate (LAS) was 10 mg l⁻¹ and for solid industrial LAS-type detergent was 50 mg l⁻¹, but washing powder did not interfere at 100 mg l⁻¹. Cationic and non-ionic detergents gave low recoveries for cobalt. Condensed phosphates at a concentration of 20 mg l⁻¹ did not cause significant interference. NTA interfered with nickel extraction and EDTA with all metals. Humic acid, however, gave no interference. A standard addition procedure can be used to correct the results.A comparison is made between the APDC-MIBK and the mixed chelate-ethyl propionate methods for the determination of trace metals in the presence of various surfactants in natural waters; the latter is preferable.     

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.     

Preliminary studies on the leaching of some trace metals from kitchen faucets

Preliminary studies were carried out on the leaching of copper, zinc, chromium, cadmium and lead from eight kitchen faucets by samples of raw, filtered and distributed Ottawa water, a sample of well water and deionized water containing 2 mg l⁻¹ aqueous fulvic acid. Leaching was effected by allowing the test solutions to stand in the inverted faucets for two successive 24-h periods. Concentrations of the metals found in the leachates were copper: first leaching, 0.12–28.0 mg l⁻¹, second leaching, 0.08-3.54 mg l⁻¹; zinc: first leaching, 0.13-10.25 mg l⁻¹, second leaching, 0.06-2.85 mg l⁻¹; chromium: first leaching, < 1.0 × 10⁻³ − 0.395 mg l⁻¹, second leaching, < 1.0 × 10⁻³−0.032 mg l⁻¹; cadmium: first leaching, < 0.05 × 10⁻³−0.01 mg l⁻¹, second leaching, < 0.05 × 10⁻³−4 × 10⁻³ mg l⁻¹; and lead: first leaching, < 0.2−110.0 mg l⁻¹, second leaching, < 0.2−82.0 mg l⁻¹. The faucets containing lead-soldered copper joints released high concentrations of lead, particularly in the case of leaching with the aqueous fulvic acid solution. Under the conditions of the present investigations it is indicated that in some cases the concentrations of metals leached could lead to intakes in excess of the maximum permissible limits for these metals. However, further investigations will be required to determine the possible contribution of these faucets to metal intake under normal usage.     

The growth inhibition of planktonic algae due to surfactants used in washing agents

A survey of inhibitory effects of nonionic and anionic surfactants, including a soap, used in washing agents, on the growth on three species of freshwater phytoplankton, Selenastrum capricornutum, Nitzschia fonticola and Microcystis aeruginosa was conducted. Based on the specific growth rate, μu estimated from a short period (2 or 3 days) cultivation of test algae, the growth inhibition was determined using EC₅₀ values where μu in the culture medium with surfactant decreased 50% of that without surfactant.The EC₅₀ values of nonionic and anionic surfactants tested here for S. capricornutum ranged from 2 to 50 mg l⁻¹ and from 10 to 100 mg l⁻¹, respectively. The tolerances of three species of algae tested with three surfactants, LAS, AE (EO:9) and soap, were different and the inhibitory effects were species specific. EC₅₀ values of LAS, AE (EO:9) and soap for S. capricornutum were 50–100, 4–8 and 10–50 mg l⁻¹, respectively. Those for N. fonticola were 20–50, 5–10 and 20–50 mg l⁻¹, and those for M. aeruginosa were 10–20, 10–50 and 10–20 mg l⁻¹, respectively.     

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.     

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.     

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.     

Combined use of calcium salts and polymeric aluminium hydroxide for defluoridation of waste waters

The combined use of calcium salt and polymeric aluminium hydroxide, P, for treatment of fluoridated waste water has been described. In the proposed method of treatment the calcium ions acts as the precipitant and polymeric aluminium hydroxide as the coagulant. At low fluoride concentrations (2 × 10⁻³ M) the precipitation reaction of calcium fluoride is a slow process. The residual fluoride concentrations found experimentally approached the theoretically predicted values only at high calcium concentrations (| F | _t/ | Ca | _I molar ratio = 0.24) and for long equilibration times. The addition of calcium fluoride seeds (approx. 20 mg 1⁻¹) accelerated the precipitation process and the results obtained for the residual fluoride concentrations were close to the theoretically calculated ones regardless of the calcium ion concentration used. Under these conditions fine CaF₂ precipitate with poor settleability was formed. The addition of small amounts of polymeric aluminium hydroxide, P, (F/Al molar ratio = 10) greatly facilitates the settleability of the precipitate. The advantage of using P over alum for the removal of fluoride is that less concentration of the former is required and the reproducibility of the results are good. The effect of sulphate on the precipitation of calcium fluoride has been also studied. Tests with fluoride containing waste water collected from aluminium industry showed that fluoride can be effectively removed.