“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.     

Effect of Complexing Agents on the Acute Toxicity of Copper to Common Guppy Lebistes reticulatus (PETERS)

The acute toxicity of copper and copper plus complexing agents to common guppy Lebistes reticulatus was studied for 96 h by a static bioassay technique. The addition of complexing agents viz. disodium salt of EDTA, citric acid, sodium thiosulphate and glycine in Cu²⁺ solutions caused a great decrease in the per-cent mortality as compared to that of Cu²⁺ test solutions alone. 10 mg/l of complexing agent was added in each copper concentration in all the test series. The 96 h LC₅₀ values and 95% confidence limits in mg/l of Cu²⁺ plus were 1.23 (0.95…1.65) for Cu²⁺ alone; 4.30 (4.04 … 4.55) for Cu²⁺ plus EDTA; 1.94 (1.69 … 2.18) for Cu²⁺ plus citric acid; 3.44 (2.96 … 3.74) for Cu²⁺ sodium thiosulphate and 2.29 (2.22 … 3.02) for Cu²⁺ plus glycine.     

“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.     

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.     

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.     

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).     

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.     

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.     

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.     

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.     

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.     

Untersuchungen über die Beeinflussung der planktischen Photosynthese durch anorganische Metallsalze im eutrophen Alpnachersee und der mesotrophen Horwer Bucht

The effects on phytoplankton photosynthesis of inorganic metal salts HgCl₂, CuSO₄, Cd(NO₃)₂, ZnCl₂ and Pb(NO₃)₂ were studied over monthly intervals. In experiments with individual metals, phytoplankton photosynthesis was not adversely affected if the concentration increase above background levels did not exceed 10^?9 mole Hg/l, 5·10^?9 mole Cu/l, 2·10^?8 mole Cd/l, 5·10^?8 mole Zn/l and 2·10^?7 mole Pb/l, respectively. However when the concentration was increased by 5·10^?10 mole Hg/l+5·10^?9 mole Cu/l+5·10^?9 mole Cd/l+5·10^?8 mole Zn/l+5·10^?8 mole Pb/l photosynthesis was significantly reduced, due to a synergetic effect of the combined metals. The influence of phytoplankton density, pH-value concentration of calcium, dissolved organic nitrogen and allochthonous debris on heavy metal toxicity was investigated. Changes in phytoplankton composition are believed to the main reason for the seasonal variation in the toxic effects of heavy metals.     

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.     

Hydrogeochemical balance of forest umbrisol profiles (‘Sierra de Gata’, central western Spain)

Three techniques for obtaining soil water solutions (gravitational and matrical waters extracted using both in situ tension lysimeters and in vitro pressure chambers) and their later chemical analysis were performed in order to know the evolution of the soil‐solution composition when water moves down through the soil, from the Ah soil horizon to the BwC‐ or C‐horizons of forest soils located in western Spain. Additionally, ion concentrations and water volumes of input waters to soil (canopy washout) and exported waters (drainage solutions from C‐horizons) were determined to establish the net balance of solutes in order to determine the rates of leaching or retention of ions. A generalized process of sorption or retention of most components (even Cl^?) was observed, from the soil surface to the C‐horizon, in both gravitational and matrical waters, with H₄SiO₄, Mn²⁺, Na⁺, and SO₄^2? being the net exported components from the soil through the groundwater. These results enhance the role of the recycling effect in these forest soils. The net percentages of elements retained in these forest soils, considering the inputs and the outputs balance, were 68% K⁺, 85% Ca²⁺, 58% Mg²⁺, 7% Al³⁺, 5% Fe³⁺, 34% Zn²⁺, 57% Cl^?, and 20% NO₃^?, and about 75% of dissolved organic carbon was mineralized. Copyright © 2007 John Wiley & Sons, Ltd.     

Die Massenentwicklung der Geißelalge Uroglena americana (Alk.) Lemm in Trinkwassertalsperren Thüringens und ihre Bekämpfung

A mass development of Uroglena americana with cellular densities of up to 13.5 · 10⁶ and 86.10⁶ cells/l, was observed in two drinking-water reservoirs. In the first case the development remained confined to the upper 20 m, in the second case there occurred a gradual shift of the maximum to deeper zones from May to July with decreasing cellular densities down to a depth of 35 m. Laboratory experiments for the control of the algae development were performed in order to protect the drinking-water resources from potential impairments of odour and taste. Samples of the storage-reservoir water with 20.10⁶ cells/l of Uroglena were concentrated up to 1.25 … 12.5 mg/l Ca(OH)₂ (pH-values of 7.2 … 9.6) by addition of calcium hydroxide and observed for 39 h. First impairment of the cells of Uroglena is detectable at 5 mg/l Ca(OH)₂ after 15 h, an immediate effect can be observed at 7.5 mg/l Ca(OH)₂ together with increased sedimentation, also Gymnodinium and Cryptomonas having been damaged. Thereupon a successful control of Uroglena by liming up to pH-values above 8.0 is possible. The application of lime to outdoor areas was not necessary, in the final analysis, since the drinking-water quality could be secured by the optimum choice of the intake depth of raw water with a maximum of 4.10³ to 77.10³ cells/l.     

Lead and copper in the waters of Raritan and Lower New York Bays

A survey of waters adjacent to this heavily urbanized and industrialized region showed concentrations of copper, 65 μg l.^?1 to be the highest reported to date for estuarine waters, and lead up to 13.9 μg l.^?1 Correlations between distributions of dissolved and total metal concentration in the water column, hydrography, and metal in the sediment were related to benthic studies in this area. Laboratory studies are cited which show the potential for adverse effects on marine animals at these metal concentrations.     

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.     

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.     

Der Einfluß von Erdölkohlenwasserstoffen auf die Primärproduktion des Donauplanktons

Danube river water samples were saturated with mineral oil, and then the primary production (gross) was determined by means of the light-dark bottle method (oxygen) in situ at depths of 0.1… 1.5 m in comparison with untreated samples. Samples were exposed for half a solar day alternately during the first and second half-days. Investigations carried out between March and October for periods of 14 days showed a mean production of 2.56 g · m^?2d^?1 O₂, which was reduced by 36% due to 12.6 mg/l hydrocarbons. Production decreases with the water depth from 6.2 to 0.9 mg · l^?1d^?1 0₂, whereas the inhibition by hydrocarbons increases from 31 to 41%.     

On‐line Solid Phase Extraction of Copper in Water Samples with Flow Injection Flame Atomic Absorption Spectrometry

An on‐line solid phase extraction method for the preconcentration and determination of Cu(II) by flame atomic absorption spectrometry has been described. The procedure is based on the retention of Cu(II) ions at pH 6.0 on a minicolumn packed with Amberlite XAD‐1180 resin impregnated with chrome azurol S. After preconcentration, Cu(II) ions adsorbed on the impregnated resin were eluted by 1 mol L^?1 HNO₃ solution. Several parameters, such as pH, type of eluent, flow rates of sample and eluent solutions, amount of resin were evaluated. At optimized conditions, for 3.5 min of preconcentration time, the system achieved a detection limit of 1.0 µg L^?1, and a relative standard deviation of 1.2% at 0.2 µg mL^?1 copper. An enrichment factor of 56‐fold was obtained with respect to the copper determination. The proposed method was successfully validated by the analysis of standard reference material (TMDA 54.4 lake water) and recovery studies. The method was applied to the preconcentration of Cu(II) in natural water samples.