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.     

Simultaneous multielement determination of trace metals in lake waters by ICP emission spectrometry with preconcentration and their background levels in Japan

An analytical method combining a preconcentration followed by determination with inductively coupled plasma emission spectrometry (ICPES) was developed for monitoring background levels of trace metals in natural waters. Complexes of trace metals (Al, Ti, V, Mn, Fe, Co, Ni, Cu, Zn, Cd and Pb) and 8-hydroxyquinoline were absorbed to a C₁₈ chemically bonded silica gel disposable plastic column. They were eluted with methanol and digested with nitric acid. With this preconcentration procedure, about 500-fold preconcentration is possible. Simultaneous multielement analysis with ICPES ensures the necessary sensitivity to measure the trace metals in Lake Mashu water at concentration ranges from μg l^?1 (ppb) to ng l^?1 (ppt).Lake Mashu is a deep oligotrophic lake in Hokkaido, Japan and famous for the highest transparency in the world. The trace metal concentrations in Lake Mashu were extremely low: Fe 2.6; Al 1.2; Mn 0.76; Zn 0.63; V 0.15; Cu 0.069; Ti 0.06; Pb 0.05; Ni 0.027; Cd < 0.006; and Co < 0.004 μg l^?1. The suitability of Lake Mashu for a background level monitoring station for global environmental pollution was assessed by the comparison to reference data for other lakes in the world.     

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.     

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.     

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.     

Anodic stripping voltammetric study of the lability of Cd, Pb, Cu ions sorbed on humic acid particles

The sorption of Cd, Pb and Cu by humic acid particles has been studied at μg l⁻¹ levels using A.S.V. on a Hg film electrode as the measuring technique. The variables examined included amount of solid present (0.01–0.2% w/v), initial metal ion concn (10–100 μg l⁻¹), systems pH (5.3, 6.35, 8.15) and base electrolyte composition. The calculated capacity for specific adsorption of the metal ions was a few mmol M²⁺ kg⁻¹, or less. The apparent lability of part of the sorbed material was examined by analysing the base solution before and after filtering, and by adding Chelex 100 particles to the suspension. Some sorbed Cd²⁺ was A.S.V. labile, another fraction transferred to the resin. The effect of solution reactions on uptake was studied by making the 1 M CH₃COONa base solution 0.2 M in a range of Na⁺ salts (8 different anions), or in carboxylic acid content (5 acids) or in compounds having S-type bonding groups. Formation of complex ions in solution altered the extent of metal ion uptake, and in the case of Cu A.S.V. peak size, shape and position were varied. It is suggested that natural waters containing suspended matter should be analysed by A.S.V. “as received”, as well as after filtration since response differences provide guidance in respect to the lability of sorbed ions.     

Phosphorus adsorption to riverine suspended matter: Implications for the P-budget of Lake Constance

Dissolved phosphorus from Lake Constance water was adsorbed by particulate matter from the Alpenrhein whenever the equilibrium phosphorus concentration of 0.85 μmol l⁻¹ was exceeded. When shaken in phosphate-free lake water the solids liberated small amounts of P (1% of the total-P). The maximum adsorption capacity of the particles was estimated to be 2.8 μmol g⁻¹ (dry substance). Only part of the phosphorus once experimentally sorbed to the solids was shown to desorbe in P-free lake water.During 1981 1.47·10⁹ kg of particulate matter was discharged into Lake Constance from the Alpenrhein. By adsorption these sedimenting materials had the potential to remove 18–25·10³ kg of dissolved phosphorus from the water column, thus comprising almost 2% of the total P-load in 1981.     

Lake restoration by dilution: Moses lake, Washington

Dilution water, low in macronutrients, was added to Moses Lake on three occasions in 1977 and once in 1978 during the spring-summer period. The addition resulted in reducing the annual average inflow concentration of phosphorus from about 130–140 μg l⁻¹ to 100 μg l⁻¹. The water exchange rate in Parker Horn, which is 8% of the lake volume, increased from about 1% day⁻¹ normally to 7 and 11% day⁻¹ for the May–September period in 1977 and 1978, respectively. Lake water was displaced at a predictable rate in the whole lake as well as the areas proximal to the input, as verified by specific conductance.Improvements in lake quality, compared to values from 1969–70, were rather good with greater reductions in algal biomass occurring than might have been expected to result from the less impressive reductions in total P content. Chlorophyll a decreased by about 60–80% and total P decreased by about 50–60%, depending on the area of the lake. However, Chl a averaged only 15 μg l⁻¹ during May–September 1978, while total P was rather high at 70–80 μg l⁻¹. The fraction of the phytoplankton composed by blue-green algae decreased from 96% in 1970 to 68% in 1977–78. The cause for the effect on biomass and species composition is unknown, but may be related to dilution of blue-green excretory products.A dilution water input of about 6 m³ s⁻¹ continuously during April–September would require 20% less total water and should provide adequate control of eutrophication in at least 30% of the lake volume proximal to the input and Parker Horn. That would provide an exchange rate of 5% day⁻¹ for Parker Horn and should achieve lake water residuals by midsummer of 50%. Two additional inputs to the lake are also proposed as two more phases in the restoration project.     

Heavy metals in animals of Lake Balaton

Hg, Cd, Cu, Pb, Zn, Fe and Mn concentrations were measured in Chironomidae larvae, Crustacea plankton, as well as in various organs of mussels and fishes collected from the open water area of Lake Balaton. The values were comparatively low. However, there were significant differences in the metal concentrations of species and tissue.Most Cd was found in the gill of Unio pictorum L., most Pb, Zn and Mn in the gill of Anodonta cygnea L., most Cu in Crustacea plankton and in the liver of Abramis brama L., and most Hg and Fe in Chironomidae larvae. Low concentrations occurred in fishes, the lowest in the flesh of Stizostedion lucioperca L.Accumulation of metals in organs as compared with their concentration in the lake water was in the range of 3.4 × 10²−2.6 × 10³ for Hg; 7.0 × 10²−6.8 × 10³ for Cd; 3.3 × 10²−9.7 × 10³ for Cu; 6.9 × 10²−8.1 × 10³ for Zn; 1.5 × 10³−2.4 × 10⁴ for Pb; 3.5 × 10²−3.1 × 10⁴ for Fe; and 5.0 × 10¹−3.5 × 10⁵ for Mn.     

Speciation (including adsorbed species) of copper, lead, nickel and zinc in the Meuse River: Observed results compared to values calculated with a chemical equilibrium computer program

The adsorption of trace metals on sediments of the Meuse River was interpreted in terms of competition between metals and protons for surface sites. Surface constants (^*β₁^surf) were determined for Cu, Zn and Cd (10^−1.8, 10^−3.6 and 10^−3.7). The constants for Pb, Ni, Ca and Mg (10^−1.7, 10^−3.8, 10^−6.5 and 10^−5.2) were estimated using a correlation between hydrolysis and surface constants. A chemical equilibrium computer program in which surface sites (for adsorption reactions) are treated as conventional ligands was used to calculate the speciation of Cu, Pb, Ni and Zn in the Meuse River. Calculated values of the adsorbed/dissolved distribution agreed well with observed values, after some realistic data manipulation. This work indicates that dissolved trace metal concentrations in the Meuse River are controlled by adsorption and not by precipitation mechanisms. The relationship between organic matter and suspended matter greatly influences the adsorption of metals like Cu and Pb.     

Total metal concentrations and partitioning of Cd, Cr, Cu, Fe, Ni and Zn in sewage sludge

Application of the BCR three-step sequential extraction procedure to sewage sludge samples collected at an urban wastewater treatment plant (Dom ale, Slovenia) is reported. The total concentrations of Cd, Cr, Cu, Fe, Ni and Zn and their concentrations in fractions after extraction were determined by flame or electrothermal atomic absorption spectrometry (FAAS, ETAAS) under optimised measurement conditions. Total acid digestion including hydrofluoric acid (HF) treatment and aqua regia extraction were compared in order to estimate the efficiency of aqua regia extraction for determination of total metal concentrations in sewage sludge. It was found experimentally that aqua regia quantitatively leached these heavy metals from the sewage sludge and could therefore be applied in analysis of total heavy metal concentrations. The total concentrations of 856 mg kg⁻¹ Cr, 621 mg kg⁻¹ Ni and 2032 mg kg⁻¹ Zn were higher than those set by Slovenian legislation for sludge to be used in agriculture. Total concentrations of 2.78 mg kg⁻¹ Cd, 433 mg kg⁻¹ Cu and 126 mg kg⁻¹ Pb were below those permitted in the relevant legislation. CRM 146R reference material was used to follow the quality of the analytical process. The results of the BCR three-step sequential extraction procedure indicate high Ni and Zn mobility in the sludge analysed. The other heavy metals were primarily in sparingly soluble fractions and hence poorly mobile. Due to the high total Ni concentration and its high mobility the investigated sewage sludge could not be used in agriculture.     

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.     

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.     

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.     

Nitrogen gas supersaturation in the recent sediments of lake erie and two polluted harbors

Nitrogen gas distributions in sediment pore water were determined for cores collected in Lake Erie and two nearby harbors. Concentrations of N₂ gas ranged from 11.9 to 37.0 ml l⁻¹ and from 8.9 to 58.3 ml l⁻¹ for open lake and polluted harbor sediments, respectively. Maximum concentrations in the harbor sediments were as high as 3.5 times N₂ saturation calculated for the overlying water. Indirect diffusive flux estimates for nitrogen gas ranged from 20 to 32% of the particulate nitrogen sedimentation rate in Lake Erie. At one location, the amount of nitrogen gas lost by diffusion was calculated to be greater than the nitrogen deposited to the sediments. Nitrogen gas production and diffusive loss from surficial sediments probably represents a major pathway for nitrogen removal from Lake Erie.     

Zinc, cadmium and lead in water, sediments and submerged plants of the Derwent Reservoir, Northern England

A partial budget is presented of the zinc, cadmium and lead entering the Derwent Reservoir. The mean levels in the water column upstream of the site of inflow are: Zn, 0.216 mg 1⁻¹ ; Cd, 0.003 mg 1⁻¹; Pb, 0.065 mg 1⁻¹; the levels after passage through the 4.1 km² reservoir fall by: Zn, 70.3%; Cd, 98.3%; Pb, 89.2%. Most of these metals are deposited in sediments, the mean values for which are: Zn, 1035 μg⁻¹; Cd, 13μg⁻¹; Pb, 827μg⁻¹. Lead, a higher percentage of which occurs as particulate material, is deposited more rapidly than zinc; this effect is especially obvious when streaming of colder water along the bottom of the reservoir takes place at the time of floods. Macroscopic plants are only occasional in this reservoir, due perhaps in part to heavy metal toxicity. Of the two most common submerged species, Nitella flexilis probably accumulates almost all of its metal content directly from the water, but the data suggest that sediments are a source of some of the heavy metals accumulated by Glyceria fluitans.     

Concentrations of radionuclides in Lake Ontario water from measurements on water treatment plant sludges

The purpose of this investigation was to compare the results of indirect measurements of radionuclide concentrations in water with those measured directly. The levels of ¹³⁷Cs and ²²⁶Ra in western Lake Ontario nearshore waters were derived from high-resolution γ-spectrometric measurements on aluminum hydroxide sludge samples obtained from four water treatment plants. The concentrations of ¹³⁷Cs evaluated by this indirect technique averaged 0.036 compared with 0.023 pCi l⁻¹ measured directly, while those of ²²⁶Ra averaged 0.047 compared with the direct measurement of 0.03 pCi l⁻¹. The concentrations of a number of other radionuclides at these locations were also calculated from the sludge γ-ray measurements.     

Mercury distribution in waters and fishes of the upper Madeira rivers and mercury exposure in riparian Amazonian populations

In this paper, the results of mercury concentrations in two abiotic compartments (river water and suspended particles) and two biotic compartments (fish and human hair) from the upper Madeira rivers of the Bolivian Amazon basin are presented. Because of the local hydrological regimes and a high deposition rate in the plain, due to the presence of a subsidence zone at the bottom of the Andean piedmont, in the dry season, the highest mercury concentrations and fluxes were not found in rivers where mining activities took place (2.25–6.99 ng l⁻¹; and 1.07–8.67 mg Hg d⁻¹ km⁻²), but at the outlet of the Andean basins exploited for their alluvial gold (7.22–8.22 ng l⁻¹; and 9.47–9.52 mg Hg d⁻¹ km⁻²). The total mercury concentrations measured in surface waters of the upper Beni basin varied during the dry season, from 2.24 to 2.57 ng l⁻¹ in the glacial waters of the Zongo river, to 7.00 ng l⁻¹ in the Madeira River at Porto Velho and 9.49–10.86 ng l⁻¹ at its confluence with the Amazon. The results obtained from fish indicate, on one hand, that 86% of the piscivorous fishes collected in the Beni river were contaminated, and, on the other hand, their high mercury concentrations could exceed by almost four times the WHO (1976) safety limit. In the Beni River, the mercury concentrations found in omnivorous and mud-feeding fish ranged from 0.02 to 0.19 μg g⁻¹ (wet wt.), and in piscivorous fish, from 0.33 to 2.30 μg Hg g⁻¹ (wet wt.). The mercury accumulated by carnivorous fishes was mainly present in its organic form; methylmercury represented 73–98% of the total mercury analysed. Eighty persons were studied in the entire Bolivian Amazonian basin. Unlike the gold miners, who are more affected by tropical diseases, such as malaria and yellow fever, the indigenous people living on the banks of the Beni river, present elevated levels of mercury (9.81 μg g⁻¹ on average). We observed an increase in contamination in young children still being breast-fed, confirming that hair mercury concentration in babies was significantly affected by maternal mercury contamination during pregnancy. These results show that the major health impacts caused by mercury affect people who are not working directly in gold mining activities but who have a regular fish diet.     

Adsorption of trace metals on aluminium oxide: A simulation of processes in freshwater systems by close approximation to natural conditions

The interaction of the trace metals Cu, Co, Zn, Ni, Pb and Cd with aluminium hydroxide precipitated in-situ from homogeneous solution was studied. Using total concentrations of 10⁻⁴ M Al, 10⁻⁷ M Zn, Cu, Co, Ni and 10⁻⁸ M Pb and Cd a removal of Zn, Cu, Pb, Cd from solution occurred together with Al, while Co and Ni concentrations in solution remained unchanged. The binding of Cu, Pb and Zn, Cd is in agreement with the effect predicted by using published (resp. evaluated for Zn and Cd), values for stability constants of surface complexes on preformed Al₂O₃-suspension. The different behaviour of these elements and of Co and Ni is expected from the hydrolysis and adsorption tendencies. The experimental conditions correspond to natural conditions in lake waters, where due to the pH-dependent solubility of aluminium hydroxide, in-situ precipitation may occur and cause the scavenging of trace elements.