Concentrations of heavy metals in small Norwegian lakes

As part of regional surveys of lakes in Norway the concentrations of Zn, Pb, Cu and Cd were measured in surface- and bottom-water samples collected from representative, small, pristine lakes (136 in southern Norway sampled in October 1974, 58 resampled in March 1975, and 77 in northern Norway sampled in March 1975). The lakes, a statistically representative sample of small lakes in Norway, were chosen such that their watersheds are undisturbed. Heavy-metal concentrations in these lakes thus reflect only natural inputs and anthropogenic inputs via the atmosphere.The generally low concentrations (Zn 0.5–12.0 μg l⁻¹; Pb 0–2.0 μg l⁻¹; Cu 0–2.0 μg l⁻¹; Cd 0.1-0.5 μg l⁻¹) measured in lakes in central and northern Norway provide estimates of natural “background” levels. These estimates may be too high because they include the global-scale deposition of heavy metals from the atmosphere which has increased as a result of industrial activities.Concentrations of Zn and Pb in lakes in southernmost and southeastern Norway lie above these “background” levels, apparently because of atmospheric deposition associated with the acidic precipitation that falls over southern Scandinavia. Increased heavy-metal concentrations in acid lakes may also be due to increased mobilization of metals due to acidification of soil- and surface-waters.     

Toxicity of silver to rainbow trout (Salmo gairdneri)

The mean 96-h LC₅₀'s of silver with rainbow trout were 6.5 μg l⁻¹ and 13.0 μg l⁻¹ in soft water (approximately 26 mg l⁻¹ hardness as CaCO₃) and hard water (350 mg l⁻¹ hardness as CaCO₃), respectively. The long-term, “no effect” concentration for silver, added to the water as silver nitrate, was between 0.09 and 0.17 μg l⁻¹ after 18 months exposure in soft water. The “no effect” concentration is that concentration range which defines no observed effect. Based on mortalities different from the control, no mortalities attributable to silver occurred at 0.09 μg Ag l⁻¹, whereas 17.2% mortality occurred to fish exposed to 0.17 μg ll⁻¹. The “no effect” concentration does not reflect possible effects of silver on spawning behavior or reproduction, since female rainbow trout will not generally reach sexual maturity before 3 yr. At silver concentrations of 0.17 μg l⁻¹ or greater, silver caused premature hatching of eggs and reduced growth rate in fry. In one experiment, the eggs were completely hatched within 10 days of exposure; whereas, control eggs completed hatching after 42 days. The prematurely erupted fry were not well developed and frequently died. The growth rate of surviving fry was greatly reduced.     

Distribution of species of Cu, Pb, Zn and Cd in a water profile of the Yarra river estuary

The behaviour of Cu, Pb, Zn and Cd in a highly stratified estuary was examined. The distribution of ionic and ‘organically bound” forms of the metals was determined by differential pulse anodic stripping voltammetry (dpasv) before and after u.v. irradiation. The two forms of the metals were compared with the water characteristics of salinity, temperature, turbidity, flow, and inorganic and organic carbon.Irradiation increased the concentration of all four elements detectable by dpasv. The greatest increase was for Cu in the 1 m depth river water which yielded 7.5 μg l⁻¹ before irradiation and 29 μg l⁻¹ after irradiation. Cu and Cd showed minimum concentrations in the seawater layer at 4 m depth, corresponding to the fresh seawater flowing upstream below the halocline. The concentrations of Cu and Cd were higher in the river water than in the underlying seawater. Zn concentration in the river water was lower than in the seawater. Relationships between the trace metal concentrations and the characteristics of the water column are not clear, but the direction of water movement is a major influence.     

Environmental chemistry of copper in Lake Monona, Wisconsin

Lake Monona, located at Madison, Wisconsin, received over 1.5 × 10⁶ pounds of copper sulfate in the past 50 yr to control excessive algal growth. Dissolved copper on Lake Monona epilimnion is inversely related to pH which indicates possible control of dissolved copper by basic copper carbonate. Concentrations as high as about 4 μg Cu l⁻¹ were found in Lake Monona epilimnion, which also contains 3.3 me l⁻¹ (milliequivalents per liter) of alkalinity, mostly bicarbonate. Concentrations of dissolved copper were consistently lower (0.3 μg Cu l⁻¹) in the hypolimnion. Sulfide probably controls dissolved copper in the hypolimnion during anoxic conditions because of sulfide insolubility. Particulate copper concentrations of about 3 μg l⁻¹ increased slightly with depth. The highest concentrations of copper in Lake Monona sediments (650 mg kg⁻¹) were found approximately 60 cm below the current sediment surface. Surface sediments of Lake Monona contained approximately 250 mg Cu kg⁻¹ sediment dry weight.     

Particulate and dissolved trace metals in Lake Ontario

Particulate metal concentrations in the nearshore waters of Lake Ontario have been determined to be 690 ng l⁻¹ for Cu; 40 ng l⁻¹ for Cd; 180 ng l⁻¹ for Ni; 1690 ng l⁻¹ for Zn; 2100 ng l⁻¹ for Mn; and 700 μg l⁻¹ for Fe. These values are considerably higher than the particulate metal concentrations in the offshore waters: 130, 8, 34, 230, 110, 260 and 9000 ng l⁻¹ for Cu, Cd, Ni, Zn, Pb, Mn and Fe respectively. In general, 50–80% of the Cu, 10–40% of the Ni, 20–60% of the Cd and >60% of the Pb in the lake water were bound to the suspended particulates. From the standing crop of the particulate metals and the estimated rates of their deposition on the lake bottom, the residence times of the particulate metals in the lake water column have been estimated to be about 0.5 yr. on the average. The suggestion is made that particulate organic matter may be an important vehicle for metal transport to the Lake Ontario sediments.     

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 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.     

Restoration of heavily polluted branches of the Shatt Al-Arab river, Iraq

In view of the desire to improve the water quality of the heavily polluted branches of the Shatt al-Arab River at the City of Basrah, it was proposed to maintain effective flushing as well as contracting sewerage system. The present study was conducted in order to examine the water quality of these branches in an attempt to evaluate the effectiveness of the proposed flushing system. It has been found that their waters contained very low levels of dissolved oxygen and relatively high amounts of both COD and BOD₅. The annual average water quality parameters for Basrah Branches were: dissolved oxygen 3.4 ppm; pH 7.67; hydrogen sulphide 1.4 ppm; ammonia 97 μg-at. N l⁻¹; COD 15.9 mg l⁻¹; BOD₅ 12.7 mg l⁻¹; dissolved silicates 202 μg-at. Si l⁻¹; dissolved reactive phosphate 13.4 μg-at. P-PO₄³⁻ l⁻¹; nitrate 10.4 μg-at. N-NO₃⁻ l⁻¹; nitrite 2.1 μg-at. N-NO₂⁻ l⁻¹ and chlorophyll-α 14.3 mg m⁻³. Based on our calculations, it has been concluded that the proposed system is effective, thus within a flushing cycle all of the above mentioned parameters will become within the acceptable values of the Shatt al-Arab water quality. Moreover, this system has no appreciable effect upon the water quality characteristics of the Shatt al-Arab River due to the fact that it discharges a high volume of water annually. However, It has been recommended to dredge the deposited sludge to a minimum depth of 50 cm.     

The crayfish as a “biological indicator” of aquatic contamination by heavy metals

Cu, Cd. Mg, Mn and Ni concentrations in whole Cambarus bartoni, trapped from Nepahwin Lake, Joe Lake and Wizard Lake, lying at distances of 10, 30 and 150 km, respectively, from the Sudbury smelters in Northeastern Ontario, showed an inverse relationship with the distance of the habitat from the emission site. Highest concentrations of Cu were observed in the hepatopancreas, Cd in the hepatopancreas and the gut, Fe and Mn in the gut, and Mg in the exoskeleton. Tissue concentrations of Ni and Zn were highly variable. Differences between males and females at each sampling site were not significant at the 5% level. The general relationship between crayfish tissue metal concentrations at the three sites was Cu > Mg > Mn > Zn > Ni > Cd. This observed relationship, except for Mg and Mn, agreed with the concentration relationship of these metals in the water and the sediments (top 10–20 cm) in the three lakes. In laboratory studies, Cu concentrations in the hepatopancreas, gills, exoskeleton and the viscera increased significantly over the control during the 4-weeks exposure to 125,250 and 500 μg Cu 1⁻¹. Hepatopancreas, in general, had the highest Cu concentration, and the exoskeleton, the lowest. Relationship between Ni exposure and the tissue Ni concentrations in the four treatments was 800 μg Ni l⁻¹ > 400 μg Ni l⁻¹ = 200 μg Ni l⁻¹ > control, while between the exposure periods and the tissue Ni concentrations was week 4 > week 1 > week 3 = week 2. Highest Ni concentrations at the end of the 4-week exposure to Ni were observed in the gut, gills and the hepatopancreas, and the lowest in the viscera. The present study suggests that Cambarus bartoni is a reliable indicator of the presence of class B and borderline elements with specific gravity > 5 in the aquatic environment. However, their value as biomonitors of variations in Cu and Ni concentrations in freshwater ecosystems is debatable.     

Acute and chronic toxicity of lead to rainbow trout salmo gairdneri, in hard and soft water

Lead was found to be highly toxic to rainbow trout in both hard water (hardness 353 mg l⁻¹ as CaCO₃) and soft water (hardness 28 mg l⁻¹. Analytical results differ greatly with methods of analysis when measuring concentrations of lead in the two types of water. This is exemplified in LC50's and maximum acceptable toxicant concentrations (MATC's) obtained when reported as dissolved lead vs total lead added in hard water. Two static bioassays in hard water gave 96-h LC50's of 1.32 and 1.47 mg l⁻¹ dissolved lead vs total lead LC50's of 542 and 471 mg l⁻¹, respectively. In a flow-through bioassay in soft water a 96-h LC50 of 1.17 mg l⁻¹, expressed as either dissolved or total lead, was obtained. From chronic bioassays, MATC's of lead for rainbow trout in hard water were between 18.2 and 31.7 μg l⁻¹ dissolved lead vs 120–360 μg l⁻¹ total lead. In soft water, where exposure to lead was initiated at the eyed egg stage of development, the MATC was between 4.1 and 7.6 μg l⁻¹. With exposure to lead beginning after hatching and swim-up of fry, the MATC was between 7.2 and 14.6 μg l⁻¹. Therefore, fish were more sensitive to the effects of lead when exposed as eggs.     

Toxicological effects of dehydroabietic acid (DHAA) on the trout, Salmo gairdneri Richardson, in fresh water

Toxicological and physiological effects of dehydroabietic acid (DHAA), a major poison to fishes in pulp and paper mill effluents, were studied by two experiments with rainbow trout, Salmo gairdneri Richardson: in the first, fish were acutely exposed for 4 days to an average DHAA concentration of 1.2 mg l⁻¹ (Exp. I) and in the second for 30 days to an average of 20 μg DHAA l⁻¹ (Exp. II).Compared to the controls, fish of Exp. I displayed a decreased relative weight of liver, an increased blood haematocrit, and increased haemoglobin as well as plasma protein concentrations. The aspartate aminotransferase activity of heart muscle was significantly elevated, as was also the lactate dehydrogenase (LDH) of white muscle tissue. In the blood plasma, the proportion of muscle type LDH activity was simultaneously increased. UDP-glucuronyl-transferase activities of liver and kidney were strongly decreased. Results suggest an increased and altered use of body energy reserves, decreased plasma volume and impaired liver function.Fish of Exp. II showed an increased relative weight of spleen. In addition, liver and gill LDH shifted towards heart-type. We conclude that 20 μg l⁻¹ is close to the “minimum effective concentration” of DHAA to rainbow trout.     

Trace metals: Cd, Cu, Pb and Zn in gelatinous macroplankton from the Northwestern Mediterranean

Gelatinous macroplankton organisms were collected in May 1984 in Villefranche-sur-Mer Bay and analysed for cadmium, copper, lead and zinc. Analyses were carried out by polarography for Cd, Cu and Pb and by flame atomic absorption for Zn. Phosphorus was also measured in the samples as a biomass parameter due to difficulties inherent in measuring dry weight of gelatinous organisms. The samples belong to the Tunicates, the Cnidarians (Hydromedusae, Siphonophores and Scyphomedusae), the Ctenophores and the Molluscs. Crustaceans living on some Tunicates were also sampled.As regards cadmium, copper and lead, mean concentrations did not show significant differences among the phyla studied: especially for Tunicates with mean values of 0.1 ng Cd μg P⁻¹, 2.0 ng Cu μg P⁻¹ and 0.9 ng Pb μg P⁻¹ and for Cnidarians with mean values of 0.5 ng Cd μg P⁻¹, 2.0 ng Cu μg P⁻¹ and 0.9 ng Pb μg P⁻¹ and for Cnidarians with mean values of 0.5 ng Cd μg P⁻¹, 2.0 ng Cu μg P⁻¹, 1.0 ng Pb μg P⁻¹. On the other hand, mean zinc concentrations were significantly lower in Tunicates (7.9 ng Zn μg P⁻¹) than in Cnidarians (36.8 ng Zn μg P⁻¹).Zinc seems to be preferentially concentrated in organisms which are rich in collagen, constituting the mesoglea, such as the Cnidarians, the Ctenophore and the gelatinous Mollusc studied, rather than in organisms rich in tunicin such as the Tunicates.     

Removal of heavy metals from electroplating rinsewaters by precipitation, flocculation and ultrafiltration

Chromium, nickel, copper and zinc can be effectively removed from electroplating rinsewaters by hydroxide precipitation, flocculation and ultrafiltration. Prior to precipitation, chromium is reduced from the hexavalent to the trivalent form by ferrous sulfate and cyanide in copper and zinc rinsewaters are oxidized by sodium hypochlorite. Minimum metal concentrations in the permeate from separate batches of chromium, nickel, copper and zinc rinsewaters were found to be, respectively, 0.17 mg 1⁻¹ Cr (T), 0.26 mg 1⁻¹ Ni, 0.30 mg 1⁻¹ Cu and 1.84 mg 1⁻¹ Zn. These solubilities are in good agreement with the theoretical solubility curves, except for copper where the formation of stable copper cyanide complexes appears to increase the solubilities at least two orders of magnitude relative to those predicted on the basis of the equilibrium constants for copper hydroxides and oxides. A simple mass balance model, assuming concentrate recycle and constant metal concentration in the permeate, is adequate for the prediction of feed and permeate concentrations as a function of the volume filtered up to a relative volume of about 0.3. Above this value, the feed concentrations are lower than predicted, apparently because of entrapment of metal precipitate in the strainer. Water recoveries are strongly dependent on the specific metal removed and are found to be 24% for Ni with a 0.20 μm membrane, 10% for Cr with a 0.80 μm membrane, 6.5% for Cu and 3.7% for Zn, both with a 0.45 μm membrane.     

Growth responses of selected freshwater algae to trace elements and scrubber ash slurry generated by coal-fired power plants

In laboratory studies, the freshwater algae Ankistrodesmus falcatus, Scenedesmus obliquus, Selenastrum capricornutum, and Microcoleus vaginatus were exposed to potential pollutants from coal-fired power plants, and their growth responses were evaluated. Using a modification of the EPA Algal Assay Procedure Bottle Test, algae were incubated in media containing As(V) as Na₂HAsO₄ · 7H₂O, Cd(II) as CdSO₄, Hg(II) as HgSO₄, Se(VI) as Na₂SeO₄, in solution, and scrubber ash slurry generated at a western U.S. coal-fired power plant complex. First significant inhibition levels as well as algistatic-algicidal levels are reported. The median effective concentration (EC50) values for the potential pollutants ranged from 0.048–30.761 mg l⁻¹ (0.00064–0.41058 M) As(V), 0.005–0.019 mg l⁻¹ (0.00004–0.00017 M) Cd(II), 0.033–0.253 mg l⁻¹ (0.00016–0.00126 M) Hg(II), 0.033–8.511 mg l⁻¹ (0.00042–0.10779 M) Se(VI), and 3.048–15.417% scrubber ash slurry extract (SASE).     

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.     

Submersible integrating water sampler for heavy metals

A simple submersible apparatus for the collection of a continuous composite water sample, suitable for heavy metal determination, is described. A comparison between results obtained for Cd, Pb, Cu, Zn and Hg using this sampler and a series of hand collected samples showed a satisfactory level of agreement. The apparatus is suitable for pollution monitoring purposes in relatively shallow (<20 m) waters where the concentrations of Cd, Pb, Cu, Zn and Hg are expected to exceed 0.05, 0.2, 0.2, 0.4 and 0.02 μg l⁻¹ respectively.     

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.     

Acute toxicity and behavioral responses of coho salmon (Oncorhynchus kisutch) and shiner perch (Cymatogaster aggregata) to chlorine in heated sea-water

The acute toxicity and behavioral response to chlorinated and heated sea-water was determined for coho salmon smolts and 1–3 month old shiner perch. LC₅₀'s were determined for 7.5, 15, 30 and 60 min exposure times; 13, 16 and 20°C (Δt = 0, 3, 7°C) temperatures and total residual oxidant (TRO) concentrations ranging from 0.077 to 1.035 mg l⁻¹. The mean 60 min LC₅₀ for shiner perch was significantly reduced (P ≤ 0.05) from 308 μg l⁻¹ TRO at 13°C to 230 μg l⁻¹ TRO at 20°C. The 60 min LC₅₀ for coho salmon decreased from 208 μg l⁻¹ TRO at 13°C to 130 μg l⁻¹ at 20°C. The LC₅₀'s for coho salmon in chlorinated sea-water averaged 55% of those for shiner perch. The relationship between TRO concentration, exposure time, and percent survival in chlorinated sea-water at 13°C is presented for both species.A significant (P ≤ 0.01) avoidance threshold for coho salmon occurred at 2 μg l⁻¹ TRO and was reinforced with increasing temperature. A significant (P ≤ 0.01) avoidance threshold for shiner perch occurred at 175 μg l⁻¹ TRO, while a significant preference (P ≤ 0.05 or 0.01) response at 16°C and 20°C occurred at 10, 25, 50 and 100 μg l⁻¹ TRO. The ecological implications of the toxicity tests and the behavioral responses are discussed.     

Chlorophenols in surface waters of the Netherlands (1976–1977)

In this paper an analytical method is described for the capillary gas chromatographic determination, after derivatization, of 19 individual chlorophenols in surface water. The minimum detectable amounts are for monochlorophenols 2 μg l⁻¹, for dichlorophenols 0.05 μg l⁻¹, for trichlorophenols 0.02 μg l⁻¹ and for tetra- and pentachlorophenols 0.01 μg l⁻¹. The results of a monitoring program in the river Rhine and other Dutch surface waters with respect to these compounds are presented. The results cover the period January 1976–December 1977. 2,6-Dichlorophenol, 2,4,6-trichlorophenol, 2,3,4,6-tetrachlorophenol and pentachlorophenol had the highest frequencies of occurrence in the river Rhine and its tributaries. Pentachlorophenol was found in the highest concentrations (up to 11 μg l⁻¹).     

The simultaneous determination of arsenic, antimony, bismuth, selenium and tellurium in waters by an inductively coupled plasma/volatile hydride method

A method using inductively coupled plasma spectrometry (ICP) and hydride generation is used to determine As, Sb, Bi, Se and Te simultaneously in both treated and natural waters. Two methods are described, direct analysis and a coprecipitation preconcentration method. Precision (RSD) was less than 10% for solutions of 1 μg l⁻¹ by using the preconcentration method. Recoveries of a wide range of analyte concentrations (0.1–50μg l⁻¹) for sea-water and internal supply water were excellent. Routine application of the method to waters from the rivers Hayle and Gannel, Cornwall are also reported.A time delay experiment was conducted to investigate the stability of the analytes in acidic solution. It was found that all the analytes in an ionic form were stable for up to 8 days.