Eliminierung von Schwermetallen aus komplexbildnerhaltigen Abwässern durch Kalk-/Kreide-Fällung

A report is given on laboratory investigations into model waters containing Cu²⁺-, Ni²⁺- or Zn²⁺-ions and tartrate, citrate, NTA or EDTA as complexing agents. There were determined residual concentrations of the metal ions at different shares of complexing agents, which are achieved by the precipitation with lime and chalk. Chalk is added in order to secure the required exess of calcium ions without causing an overalkalinization of the water. In the range of pH = 8…9, however, residual concentrations lower than 1 mg/1 are achieved only for copper ions in the presence of tartrate.     

Effect of Zinc,Copper and Mercury on Channa marulius (HAMILTON)

Static bioassay acute toxicity tests of Zinc, Copper and Mercury were conducted to determine the median lethal concentrations (LC₅₀s) of a freshwater teleost Channa marulius (HAM .) The 96 h LC₅₀ and 95% confidence limits for Zn²⁺ were 25.61 (24.13 … 27.12) mg/l; 0.90 (0.80 … 1.038) mg/l; for Cu²⁺ and 0.314 (0.257 … 0.371) mg/l for Hg²⁺. However, these values decreased at 240 h of exposure and were: 21.09 (18.29 … 24.60) mg Zn²⁺/l; 0.66 (0.568 … 0.841) mg Cu²⁺/l; and 0.131 (0.103 … 0.158) mg Hg²⁺/l. The relative potency ratio of Zn/Hg, Zn/Cu and Cu/Hg suggests that fish were most sensitive to Hg, followed by Cu and Zn ions. The acute toxicities of mixtures of Zn²⁺?Cu²⁺; Zn²⁺?Hg²⁺, Cu²⁺?Hg²⁺ and Zn²⁺?Cu²⁺?Hg²⁺ up to 48 h of exposure were also investigated. The additive index and ranges for Zn²⁺?Cu²⁺ were ?0.241 (-0.577 … 0.054); 0.056 (-0.269 … 0.475) for Zn-Hg; 0.285 (-0.043 … 0.718) for Cu-Hg; and -0.542 (-1.215 … 0.005) for Zn-Cu-Hg. All the mixtures tested showed a greater than additive toxicity because index ranges overlapped zero.     

Der Einfluß der Komplexierung auf die Kupfertoxizität bei Blaualgen

Some aspects of the influence of copper speciation on toxicity for blue-green algae are reviewed. The experimental part concentrates on Oscillatoria redekei and Aphanizomenon gracile. The two investigated species produce strong extracellular copper complexing ligands: Oscillatoria redekei in the exponential and stationary growth phase, and Aphanizomenon gracile has a distinct detoxification capacity. The detoxification of copper by synthetic agents was investigated using ethylene-diamine-tetraacetic acid. Simultaneous addition of Cu²⁺ and Na₂EDTA gives evidence for a slow complexation reaction. Hence an excess of Na₂EDTA is necessary for a fast and complete detoxification of copper. Model calculations are reported to show that the precipitation of copper compounds is not probable under the conditions used.     

Acute Toxicity of Mercury,Copper and Zinc to a Freshwater Pulmonate Snail,Lymnaea luteola (LAMARCK)

The short-term toxicity of mercury, copper and zinc was studied using a freshwater pulmonate snail, Lymnaea luteola (LAMARCK ). The median period of survival increases with decreasing the toxicant concentration. The 96 h LC₅₀ values and their confidence limits were 0.135 (0.112 … 0.186) ppm of Hg²⁺; 0.172 (0.118 … 0.355) ppm of Cu²⁺; and 6.13 (5.73 to 7.19) ppm of Zn²⁺. The relative potency ratio indicates that the Hg²⁺ ions were most toxic, followed by Cu²⁺ and Zn²⁺ ions.     

Comparative Toxicity of Heavy Metals and Interaction of Metals on a Freshwater Pulmonate Snail Lymnaea acuminata (Lamarck)

In static bioassays the toxicity of heavy metal ions against Lymnaea acuminata over 24 … 96 h is tested. The values of the LC_50,96h for the metals tested are, in mg/l: Hg²⁺ ?0.023; Cu²⁺-0.034, Cd²⁺ ?0.872, Ni²⁺ ?2.78, Cr⁶⁺ ?5.97 and Zn²⁺ ?10.49. In the combined solutions of Cu²⁺, Ni²⁺ and Zn²⁺ at least an additive effect of toxicity occurs in the presence of two metals. The same holds for the presence of the three metals; in this case, the relative toxicity against the mixture of two metallic salt solutions appears to be slightly reduced. The acute manifestation of the toxic effect occurs within 48 h, subsequently the relative mortality decreases especially in the mixed solutions.     

Toxicity of Interactions of Zinc —Nickel,Copper —Nickel and Zinc —Nickel —Copper to a Freshwater Teleost,Lebistes reticulatus (PETERS)1

The lethal toxicity of mixtures of Zn²⁺ —Ni²⁺, Cu²⁺ —Ni²⁺ and Zn²⁺ —Cu²⁺ —Ni²⁺ to common guppy at 21£C in hard water (total hardness = 260 mg/l as CaCO₃) was studied under static bioassays test conditions with renewal of the test solutions every 24 h. The heavy metals were tested separately and in mixtures. The 48 h median lethal concentrations (LC₅₀) for individual salts were 75 mg/l Zn²⁺, 37 mg/l for Ni²⁺ and 2.5 mg/l for Cu²⁺. Concentrations were expressed in “toxic units” by taking them as proportions of LC₅₀ values. Experiments showed that in the Zn²⁺-Ni²⁺ mixture, when Ni²⁺ was more in proportion, the toxicity was more than additive. The 48 h LC₅₀ value and 95% confidence limits in the Ni²⁺-Cu²⁺ mixture were 0.684 (0.484 … 0.807) toxic units and the mixture produced more than the additive toxicity (synergism.). The LC₅₀ value and its 95% confidence limits in a Zn²⁺?Cu²⁺?Ni²⁺ mixture also suggested that the mixture was again strictly additive. The results indicate that heavy metallic mixtures would pose a greater toxicological danger to fish than the respective individual metals.     

Effect of lethal concentrations of copper on Mystus bleekeri (day)

In the batch test with daily exchange of medium the effect of copper ions at 2.4 mmol/l (Ca²⁺ + Mg²⁺) over 10 d of exposure is investigated. The LT₅₀ values and 95% confidence limits at 3.7, 2.1 and 1.0 ppm of Cu were 26.7 (23.6… 29.9), 47.5 (39.6… 57.0) and 101.5 (78.5… 130.7) h, respectively. The LC₅₀ values of copper in ppm were 4.05 (24 h), 1.69 (48 h), 0.829 (9.96 and 0.776 (240 h).     

Studies on Separation of Heavy Metals from Acidic Solutions by Foam Fractionation with Respect to an Application on Acidic Soil Extracts

An experimental investigation is presented on the batch foam fractionation of the heavy metal cations Pb²⁺, Cd²⁺, Cu²⁺, Sb³⁺ and As⁵⁺ from diluted aqueous solutions with hexamethylenedithiocarbamate (HMDC) as complexing agent and sodiumdodecylsulfate (SDS) as surfactant. Among the considered pH-values of 2,4 and 7 the pH 2 experiments allow a direct application of foam fractionation on acidic extracts from heavy metal contaminated soil. The experiments at pH 2 and pH 4 show better results than those at neutral pH. Although a simple device was used, a maximum enrichment factor of 13.8 and a minimum removal factor of 0.01 have been measured. The flotation with weak organic acids like citric acid (CA) and acetic acid (AA) show about 50–70% smaller enrichment factors than those acidified with hydrochloric acid. The dissolution and mixing of the reacting components as well as the concentration of the detergent and the gaseous volume flow can be regarded as basic parameters of foam fractionation.     

Comparison of the behavioural and acute toxicity of copper to sheepshead,Atlantic croaker and pinfish

Sheepshead (Archosargus probatocephalus), Atlantic croaker (Micropogon undulatus) and pinfish (Lagodon rhomboides) were each exposed to aqueous solutions of reagent grade cupric chloride in artificial seawater in four static bioassays. The 24, 48, 72 and 96-h TL_m were determined to be, respectively, 4.17, 3.02, 2.19 and 1.14 mg Cu²⁺·I^?1 for sheepshead, 9.15, 7.55, 7.20 and 5.66 mg Cu²⁺·I^?1 for croaker, and 7.33, 4.43, 4.14 and 2.75 mg Cu²⁺·I^?1 for pinfish. These results are compared with literature values of experimental concentrations of copper producing subtle behavioural changes in these species.     

The Chemical Background of Eutrophication in the Skalka-Reservoir

Through a power plant an inflow of considerably heated and very eutrophic water gets into the polymikt reservoir (volume h 15.1 · 10⁶m³, 341 ha, MQ6 m³/s). Phosphorus is the limiting nutrient with a relatively high share from agricultural utilization. The spring maximum of phytoplankton is due to chlorophytes and diatoms, and the summer maximum is caused by cyanophyceae (up to 300 colonies/ml). It could be successfully controlled by copper sulphate. This treatment did not produce any negative effects in the free water (0.05 … 0.1 mg/l Cu²⁺) or in the sediment with a storage of about 1 t Cu per year. The construction of preimpoundment reservoirs, however, must be recommended for a lasting solution.     

Response of a Freshwater Ostracod (Cypris subglobosa SOWERBY) Exposed to Copper at Different pH Levels

Short-term tests of the acute toxicity of Cu²⁺ (from copper sulphate) to a freshwater ostracod, Cypris subglobosa SOWERBY were carried out at five different pH values from 5.5 to 8.5. The toxicity of copper abruptly decreased with an increase in pH of the Cu-containing medium. The 48 h EC₅₀ value of Cu increased from 0.35 ppm at pH =5.5… 5.1 ppm at pH =8.5. The per cent survival, median period of immobilization (ET₅₀), slope functions and the 95 per cent confidence limits were determined at each pH level. The direct correlation between EC₅₀ value and pH indicated that the acute toxicity of Cu decreased as the pH increased from 5.5… 8.5.     

“Man and the Biosphere”-Studies on Sikkim Himalayas. Part 1: Acute Toxicity of Copper and Zinc to Common Carp Cyprinus carpio (Linn.) in Soft Water

In the daily exchange of the medium with only 7.1 mg/l Ca²⁺ and 0.7 mg/l Mg²⁺ during the batch experiment the LC_50,96h for Cyprinus carpio is 0.063 mg/l Cu²⁺ and 3.12 mg/l Zn²⁺ at water temperatures of 11 to 14°C. Significant differences in mortality as referred to the LC_50,12h occur for copper only after 72 h of exposure and for zinc after 48 h of exposure. The values of LC_50,96h are clearly lower for both metals in the investigations described than most data given in literature for different fish species.     

“Man and Biosphere” — Studies on Sikkim Himalayas. Part 2: Acute Toxity of Mixed Copper-Zinc Solutions on Common Carp,Cyprinus carpio (LINN.)

In batch experiments for 6 to 48 h, individuals of Cyprinus carpio (2 g individual weight) were exposed to mixed solutions of copper and zinc sulphate: pH = 6.3, temperature 15 °C, 6.8 mg/l O₂, 7.1 mg/l Ca²⁺, 0.7 mg/l Mg²⁺. The LC₅₀ for the individual substances on exposures of 24 and 48 h amount to 9.04 and 7.28 mg/l, resp., of Zn and 0.11 and 0.095 mg/l, resp., of Cu. The sum of the biological activity of the two kinds of metal ions is assessed according to MARKING'S index: at low concentrations of the mixed solutions the two metals show an additive effect, at higher concentrations a synergistic effect occurs.     

Synthesis of Cu-binding proteins in different tissues of mussels exposed to the metal

The results demonstrate that Cu²⁺, when present in sea water at the sublethal concentration of 0.08 ppm, is able to induce, within 48 h, the synthesis of Cu-binding proteins having a molecular weight similar to that of the metallothioneins (12 000), in the gills and in the mantle of the mussels. In the digestive gland of the animals, part of the copper present in the cells is always associated to soluble low molecular weight thionein-like proteins; the level of these copper-binding proteins increases greatly in the mussels exposed to Cu²⁺. In addition, it has also been shown that an extremely low concentration of copper (0.015 ppm)—similar to the Cu²⁺ concentration found in polluted coastal areas—is able to stimulate the synthesis of thionein-like Cu-binding proteins in the three tissues examined within 2–5 days.     

Zytotoxikologische Untersuchung von Schadstoffen und Wasserblüten mit gefrierkonserviertem Bullensperma (Spermatest)

The method is based on the determination of the number of the nonmotile sperms and/or the lethally damaged sperms with the aid of the fluorescent dye primuline. Incubation takes place at a suspension density of 10.000/mm³… 38.000/mm³, at 40°C or 46 °C for 15… 60 min. During the test with sublimate the loss of motility amounts to 55% at 4 mg/l Hg²⁺, the LC₅₀ is 7.3 mg/l Hg²⁺. Phenyl-mercuric acetate causes the total loss of motility with 20 mg/l, the LC₅₀ is above 168 mg/l (equivalent to 100 mg/l Hg²⁺). The LC₅₀ of sodiumpentadecylmonosulphonate and dodecylpyridinchloride are 11.6 and 15.8 mg/l, resp. Filtrates of blooming of cyanophyceae on Baltic, having been digested by repeated freezing and thawing, with 1.5… 6.4 g/l dry matter showed motility losses of 30… 100 % for Nodularia spumigena, whereas no significant effect was produced by a filtrate of Microcystis aeruginosa with 28.2 g/l dry matter as well as water-blooming of Nodularia spumigena from the Small Jasmund Bodden.     

Acute toxicity of copper to sea catfish

Sea catfish (Arius felis) were exposed to aqueous solutions of reagent grade cupric chloride in artificial seawater ($\text{30.0±2.0‰}$, 21–23°C) in four static bioassays. The 24, 48, 72 and 96 h LC₅₀ were calculated and found to be 5.43, 4.17, 3.57 and 2.40 mg l.^?1 copper, respectively. Experimental concentrations of copper producing subtle behavioral changes in this species correspond to less than 0.3% of the 72 h LC₅₀. Based on this comparison with literature values, a new, maximum ‘safe’ concentration for copper in marine waters of 0.01 mg l.^?1 is proposed.     

Complexing capacity of the nutrient medium and its relation to inhibition of algal photosynthesis by copper

The toxic effect of copper on phytoplankton production is investigated in waters having different complexing capacities. It is demonstrated that a water’s complexing capacity does not guarantee that an equivalent amount of copper could be tolerated without adversely affecting algal production. Possible explanations for these findings are offered and discussed. It is deduced that ionic copper probably is already toxic to planktonic algae at concentrations of about 10^?10 mole/l.     

Removal of Cu2+ and Pb2+ Ions Using CMC Based Thermoresponsive Nanocomposite Hydrogel

In this study, carboxymethylcellulose (CMC) based thermoresponsive nanocomposite hydrogel was synthesized for the removal of Cu²⁺ and Pb²⁺ ions from aqueous solutions. To prepare nanocomposite hydrogel, graft copolymerization of N‐isopropyl acrylamide (NIPAm) and acrylic acid (AA) onto CMC was carried out in Na‐montmorillonite (MMT)/water suspension media and ammonium persulfate (APS) used as initiator. The chemical structures of hydrogels were characterized by Fourier transform infrared (FT‐IR) and X‐ray diffraction spectroscopy (XRD). Lower critical solution temperature (LCST), pH responsivity, swelling, and deswelling properties of the hydrogels were also examined. In addition competitive and non‐competitive removal of Cu²⁺ and Pb²⁺ studies were carried out. According to heavy metal sorption studies results, removal capacities of nanocomposite hydrogel for both metal ions were found to be higher than those of pure hydrogel. The analyzed adsorption data showed that the adsorption process of Cu²⁺ and Pb²⁺ could be explained by pseudo‐second order kinetic model. Moreover, according to competitive sorption studies, it is found to be that both hydrogels are more selective to Cu²⁺ ion rather than Pb²⁺.     

Copper- and iron-induced injuries in roots and rhizomes of reed (Phragmites australis)

About 1 mg/g dw Cu²⁺ and 8 mg/g dw Fe²⁺ were found in roots of reed plants when fed with heavy metal concentrations of 100 μM Cu²⁺ and 10 mM Fe²⁺ under hypoxia. Roots seemed to act as a kind of filter since the amounts in rhizomes were only 0.06 mg Cu²⁺/g dw and 2 mg Fe²⁺/g dw. Increased contents of both ions reduced posthypoxic respiration capacity by 40–50% and also the sum of adenylates (ATP, ADP, AMP) by the same order of magnitude, although energy charge values remained above 0.85 in Cu²⁺ and 0.79 in Fe²⁺ treatments. Energy metabolism of rhizomes was not affected. Copper and iron contents of roots as well as of rhizomes were high enough to induce oxidative stress when roots were fed with 40 μM Cu²⁺ and 1 mM Fe²⁺, respectively.From our results we conclude that increased, but environmentally attainable, amounts of copper and reduced iron ions disturb root energy metabolism, and therefore root functioning and development. Latent injuries, based on oxidative stress, may be harmful for roots and rhizomes under long term exposure.