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.     

The toxic effects of trinitrotoluene (TNT) and its primary degradation products on two species of algae and the fathead minnow

The effects of alpha trinitrotoluene (alpha TNT) and its primary degradation product (TNTcc), commonly referred to as “pink water”, were determined on members of two trophic levels. The growth responses of the algae Selenastrum capricornutum and Microcystis aeruginosa were examined through static bioassays. Death and behavioral responses of the fathead minnow (Pimephales promelas) were determined using a proportional diluter. Alpha TNT and TNTcc were both more toxic to the fathead minnow than to either species of alga. Five and 15 mg l⁻¹ alpha TNT inhibited S. capricornutum and M. aeruginosa growth, respectively. TNTcc inhibited S. capricornutum growth at concentrations above 9 mg l⁻¹; it was lethal to M. aeruginosa at 50 mg l⁻¹, but stimulated growth at lower concentrations. The 96-h lc₅₀ values based on the death response of the fathead minnow to alpha TNT and TNTcc were 2.58 and 1.60 mg l⁻¹, respectively. The 96-h ec₅₀ values based on the behavioral responses were 0.46 and 0.64 mg l⁻¹, respectively. There was no response to concentrations of 0.05 mg l⁻¹ alpha TNT and 0.07 mg l⁻¹ TNTcc.     

Toxic effects of hexavalent chromium on brook trout (Salvelinus fontinalis) and rainbow trout (Salmo gairdneri)

Exposing brook trout to various concentrations of chromium [Cr(VI)] for up to 22 months (including reproduction) significantly increased alevin mortality at 0.35 mg Cr l⁻¹ and retarded growth of young brook trout at the lowest concentration tested (0.01 mg Cr l⁻¹). Eight month exposures of rainbow trout significantly increased alevin mortality at 0.34 mg Cr l⁻¹ and also retarded growth at the lowest concentration tested (0.10 mg Cr l⁻¹). Exposures of brook trout lasting 22 months showed, however, that growth was only temporarily affected, and therefore, it was not used as an end point to measure the affects of chromium on either species. Reproduction, and embryo hatchability of brook trout were unaffected at Cr(VI) concentrations that affected survival of newly hatched alevins. The maximum acceptable toxicant concentration (MATC) for brook and rainbow trout exposed to Cr(VI) in water with a hardness of 45 mg l⁻¹ (as CaCO₃) and a pH range of 7–8 lies between 0.20 and 0.35 mg Cr l⁻¹. The 96-h lc₅₀ for brook and rainbow trout was 59 and 69 mg Cr l⁻¹, respectively: therefore, the application factor (MATC/96-h lc₅₀) for both species lies between 0.003 and 0.006.     

The toxic effect of copper on algae and rotifers from a Soda Lake (Lake Nakuru, East Africa)

The effect of Cu(II) ions on the photosynthetic oxygen production of the phytoplankton, the growth rate of the blue-green algae Spirulina platensis and the population of rotifers (Brachionus sp.) in water from the soda lake Nakuru in Kenya was investigated experimentally. The photosynthetic production was reduced to 80% of the control by the addition of 0.1 mg Cu l⁻¹ and 50% by addition of 0.15–0.20 mg Cu l⁻¹. The growth rate of Spirulina platensis was more affected by copper than the photosynthesis of phytoplankton. Addition of 0.05 mg Cu l⁻¹ reduced the growth rate to about 40% of the control. The rotifiers were less sensitive to copper than the algae, but after 8 days exposure to 0.5 mg Cu l⁻¹ or more the population was severely affected.     

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.     

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.     

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.     

Modified curcumin and dianthrimide methods for the determination of boron in the presence of high levels of nitrate and organics

Modifications have been made to the curcumin and 1,1′-dianthrimide methods for boron analysis so that they may be used in the presence of up to 700 mg l⁻¹NO⁻₃ and 500 mg l⁻¹ organic carbon. In the curcumin method, nitrate is removed by alkaline reduction using a slurry of aluminum powder. In the dianthrimide method, nitrate up to 1000 mg l⁻¹NO⁻₃ is removed in the dehydration-with-sulfuric-acid step; organics are most conveniently removed by treatment of the dehydrated sample with solid potassium persulfate. With dianthrimide, an automated procedure is used for the colour formation and measurement steps.     

The removal of chromium(VI) from dilute aqueous solution by activated carbon

The removal of chromium(VI) by activated carbon, filtrasorb 400, is brought by two major interfacial reactions: adsorption and reduction. Chemical factors such as pH and total Cr(VI) that affect the magnitude of Cr(VI) adsorption were investigated. The adsorption of Cr(VI) exhibits a peak value at pH 5–6. The particle size of carbon and the presence of cyanide species do not change the magnitude of chromium removal. The reduced Cr(VI), e.g. Cr(III) is less adsorbable than Cr(VI).The free energy of specific chemical interaction, ΔG^chem was computed by the Gouy-Chapman-Stern-Grahame model. The average values of ΔG^chem are −5.57 RT and −5.81RT, respectively, for Cr(VI) and CN. These values are significant enough to influence the overall magnitude of Cr(VI) and CN adsorption. Results also indicate that HCrO⁻₄ and Cr₂O²⁻₇ are the major Cr(VI) species involved in surface association.     

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

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

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.     

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.     

The toxicity of various mining flotation reagents to rainbow trout (Salmo gairdneri)

Preliminary testing of eight collectors (xanthates) and four frothers in 96-h static and 28-day flow-through bioassays using rainbow trout as the test organism show a great disparity in the toxicity of the chemicals administered in these two ways.For the short-term tests, the relative toxicity of the compounds is expressed as an lc₅₀ or as a range of concentration in mg l⁻¹ in which the lc₅₀ is expected to fall. Of the collectors tested in this way sodium ethyl and potassium amyl xanthate were the most toxic, with lc₅₀'s in the range of 30–50 mg l⁻¹. Among the frothers, xylenol (cresylic acid) was found to be the most toxic (5.6 mg l⁻¹ >lc₅₀ > 3.2 mg l⁻¹) while polypropylene glycol was least toxic (lc₅₀ > 1000 mg l⁻¹).The long-term tests using potassium ethyl, sodium isopropyl, sodium ethyl, and potassium amyl xanthate indicated that in the flow-through system, the toxicity of the chemicals was in the order of 100 fold greater compared with the static bioassay results.     

An evaluation of the potential toxicity of treated bleached kraft mill effluent to striped bass (Morone saxatilis walbaum) larvae exposed through metamorphosis to the juvenile stage

Twenty-day-old striped bass (Morone saxatilis) larvae were exposed to a range of treated bleached kraft mill effluent (BKME) concentrations from 0 to 20% effluent by volume (v/v) under continuous flow test conditins. The experimental test concentrations in the 2–20% BKME test aquaria had a BOD₅ which ranged from < 1 to 5 mg l⁻¹, TSS 12–17 mg l⁻¹, and true color 35–416 mg l⁻¹. Bleached kraft mill effluent did not kill larvae exposed to it for 20 days through metamorphosis to the juvenile stage. The BKME did not alter growth in length, weight or condition factor in larvae over the 20-day exposure period as determined by multiple regression analysis. A linear regression analysis on the dry weight data at Day 20 only, however, indicated a trend of decreasing weight with increasing BKME concentration. Effluent-exposed larvae also developed normally during the 20-day study. All individuals examined completed the transformation from postlarvae to juveniles by the age of 40 days.     

Role of aquatic plants in wastewater treatment by artificial wetlands

This report describes investigations using artificial wetlands which quantitatively assess the role of each of three higher aquatic plant types, Scirpus validus (bulrush), Phragmites communis (common reed) and Typha latifola (cattail), in the removal of nitrogen (via sequential nitrification-denitrification), BOD and TSS from primary municipal wastewaters. During the period August 1983–December 1984, the mean ammonia concentration of 24.7 mg l⁻¹ in the primary wastewater inflow (hydraulic application rate = 4.7 cm day⁻¹) was reduced to mean effluent levels of 1.4 mg l⁻¹ for the bulrush bed, 5.3 mg l⁻¹ for the reed bed and 17.7 mg l⁻¹ for the cattail bed, as compared to a mean value of 22.1 mg l⁻¹ for the unvegetated (control) bed. For all three vegetated beds, the mean effluent ammonia values were significantly below that for the unvegetated bed and for the inflow. The bulrushes and reeds (in that order) proved to be superior at removing ammonia, both with mean effluent levels significantly below that for the cattail bed. The high ammonia-N (and total N) removal efficiencies shown by the bulrush and reed beds are attributed to the ability of these plants to translocate O₂ from the shoots to the roots. The oxidized rhizosphere so formed stimulates sequential nitrification-denitrification. Similarly BOD removal efficiencies were highest in the bulrush and reed beds, both with mean effluent BOD levels (5.3 and 22.2 mg l⁻¹, respectively) significantly below that for the unvegetated bed (36.4 mg l⁻¹) and equal to or better than secondary treatment quality (30 mg l⁻¹). Our results demonstrate that higher aquatic plants can indeed play a significant role in secondary and advanced (N removal) wastewater treatment by wetland systems, a role that is completely distinct from that associated with their pollutant uptake capacity.     

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.     

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.     

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.     

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.     

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).