Relationships between lake chemistry and calcium and trace metal concentrations of aquatic invertebrates eaten by breeding insectivorous waterfowl

Ca, P, Al, and trace metal (Cu, Ni, Zn, Cd, and Pb) concentrations were measured in several aquatic invertebrate taxa used as food by breeding insectivorous waterfowl, sampled from three sites in eastern Canada with widely varying water chemistry. Ca concentrations were highest in molluscs (snails and clams), averaging 200-300 mg g(-1) (shells included). Aquatic insects of varying sizes, life stages and habits (caddisfly larvae, dragonfly larvae, adult backswimmers, waterstriders, and whirligig beetles) had much lower mean Ca concentrations, ranging from about 0.6 mg g(-1) (beetles) to 1.8 mg g(-1) (caddisflies). Invertebrate-Ca concentrations decreased with increasing body mass for several taxa, with smaller and larger individuals providing similar absolute amounts of Ca. Ca concentrations in most aquatic insects (but not molluscs) were reduced under acidic, low Ca, high Al, low dissolved organic carbon (DOC) and/or low total phosphorus (TP) conditions. In stepwise multiple regressions, pH was consistently the main factor explaining variability in invertebrate-Ca, after controlling for the negative relationship between invertebrate-Ca and body mass for some taxa. Molluscs were absent from lakes below pH 5.3. In general, concentrations of P and metals in invertebrate taxa were not significantly correlated with lake pH. Levels of Al, Cd, or Pb were not sufficiently high to be considered toxic to potential consumers of these organisms. For waterfowl and other birds breeding in acid-stressed habitats and relying on aquatic invertebrates as a source of food, a reduced availability of dietary Ca is more likely than an increased exposure to toxic metals to negatively affect reproductive success, especially when other adverse effects of acidification (lower diversity of prey) are considered.     

The chronic toxicity of aluminium, cadmium, mercury, and lead in birds: a review

The toxicity of chronic dietary metal exposure in birds is reviewed. It is concluded that significant physiological and biochemical responses to such exposure conditions occur at dietary metal concentrations insufficient to cause signs of overt toxicity. Particularly important are reproductive effects which include decreased egg production, decreased hatchability, and increased hatchling mortality. Young, growing birds are typically more sensitive to the toxic effects of chronic metal exposure than adults, and altricial species are often more sensitive than precocial species. Factors which modify the absorption and toxicity of heavy metals, such as Se for the case of Hg, and Ca for the case of Pb and Cd, are discussed. Monitoring strategies for assessing environmental metal exposure in birds are evaluated.     

The effects of acidification on the geochemistry of Al, Cd, Pb and Hg in freshwater environments: a literature review

Acidification of freshwater environments (terrestrial, surface water, and freshwater sediment) can significantly affect the geochemistry of Al, Cd, Pb and Hg; for example, metal mobility within soils (Al, Cd), the relative distribution of dissolved metal species (Al, Cd, Pb, Hg), and the sedimentation rate of metals in standing water bodies (Cd, Pb) can be altered by acidification. In this critical review of the literature over the last decade concerned with the interaction of acidification with these four metals, we have attempted both to provide an assessment of the current state of knowledge in this field and to emphasize those areas where significant progress has been made since the possible implications of environmental acidification on metal geochemistry became widely appreciated in the late 1970s. We have also indicated those areas which we feel are most in need of further research.     

Grit ingestion as a source of metal exposure in the spruce grouse, Dendragapus canadensis

The objective of this study was to determine if ingestion of grit was a source of metal exposure to the spruce grouse, Dendragapus canadensis. A secondary objective was to assess whether grit could provide a supplemental source of essential minerals to their diet. Ca, P, Mg, S, Zn, Cu, Ni, Co, Cr, Fe, Mn, Al, Pb and Cd of liver (adult, yearling, chicks), crop and gizzard contents (adults) were determined for grouse collected from a relatively pristine boreal forest region of north-central Ontario, Canada. With the exception of Cd liver, concentrations were independent of age [one-way analysis of variance (ANOVA); p>0.004). Zn liver concentrations tended to be greater in adults than yearlings and chicks (one-way ANOVA; p=0.02). Liver concentrations of Cd increased with age (r=0.99; p<0.001). The contribution of crop items to total gizzard elemental content was element specific; crop contents contributed 90-100% of Mn and Zn, 70% for P and Ca, 60% for Pb, 50% for S, and 0-25% for Cu, Mg, Ni, Al, Fe, Co, Cr and Cd to the total elemental concentration of gizzard contents (crop plus grit). Incorporation of grit by grouse could, therefore, constitute an important source of essential macro-(Ca, P, Mg, S) and trace elements (Cu, Fe) but not for Mn or Zn. However, in addition to providing nutrients to the bird, ingestion of grit results in exposure to toxic trace metals such as Cd which in turn is accumulating in the liver. Research directed at determining grit turnover time, and hence metal exposure rates, in bird species which ingest grit to aid in food digestion is required. The toxicological significance of Cd exposure to grit-ingesting birds needs attention.     

Changes in trace metal concentrations in lake water and biota during experimental acidification of Little Rock Lake, Wisconsin, USA

Little Rock Lake, a small (18 ha), low-alkalinity (25 microeq litre(-1), pH 6.1) seepage lake in northern Wisconsin, was divided into two basins by a flexible, inert barrier and, beginning in spring 1985, the north basin was acidified in three 2-year steps to pH 5.6, 5.1 and 4.7. The annual average pH of the reference basin remained near 6.1. As part of a comprehensive programme to determine the chemical and biological responses to acidification, minor metals (Al, Fe, Mn) and trace metals (Cd, Cu, Pb, Zn) in lake water (0.4 microm pore filtered samples), periphyton, zooplankton, and yellow perch (Perca flavescens) were measured. At pH 5.6, dissolved Mn and Fe increased in the acidified basin. At pH 5.1 and 4.7, dissolved Al, Fe, Mn, Cd and Zn were elevated in the acidified basin. At pH 4.7, dissolved Pb in the acidified basin became elevated over reference basin levels. Dissolved Cu remained similar in both basins down to pH 4.7. Cd burdens in periphyton collected on artificial substrates were lower in the treatment basin at pH 5.1 (1.8 microg g(-1) dry wt.) than in the reference basin at pH 6.1 (7.5 microg g(-1) dry wt.), but Al and Fe burdens in periphyton were similar in both basins. Likewise, Cd levels in muscle tissue of perch from the treatment basin at pH 4.7 were lower (26 ng g(-1) dry wt.) than in the reference basin at pH 6.1 (36 ng g(-1) dry wt.); Al and Fe burdens were similar in perch muscle tissue from both basins. Levels of Cd and Fe in zooplankton from the acidified basin at pH 4.7 were approximately equal to 2x higher than in animals from the reference basin. In both basins of the lake, Al and Cd levels in lake biota decreased with increasing trophic level, demonstrating that food chain biomagnification does not occur for these metals.     

Influence of reduced dietary calcium on the accumulation and effects of lead, cadmium, and aluminum in birds

The influence of low dietary calcium on the accumulation and effects of dietary lead, cadmium and aluminum was examined in zebra finches and ring doves. In zebra finches fed a diet containing 0.3% Ca, the hepatic and renal accumulation of lead was enhanced approximately 400% and of cadmium about 150-200%, compared to birds fed a 3.0% Ca diet. Low dietary Ca also caused bones of female finches to lose an average of about 60% of their normal Ca content. Loss of bone-Ca was also observed in male finches, but was less than in females. In reproductively active ring doves, low (0.4%) dietary Ca enhanced the accumulation of lead and cadmium, but not of aluminum, compared with accumulation in doves consuming a 2.0% Ca diet. Enhanced accumulation of lead and cadmium was accompanied by increased synthesis of the metal-binding protein metallothionein and by greater inhibition of delta-aminolevulinic acid dehydratase activity. These results indicate that, under conditions of reduced dietary Ca availability, such as can occur in acid-impacted environments, wild birds risk increased uptake of certain toxic metals and may accumulate toxic concentrations of these metals more rapidly. Researchers should take account of dietary Ca levels when interpreting results of dosing studies in which metals such as lead and cadmium are administered to birds.     

Partitioning of Cd and Pb in the blood of European blackbirds (Turdus merula) from a smelter contaminated site and use for biomonitoring

Blood composition is commonly measured to assess exposure to and effects of metals on birds. In most of passerine species, only small volumes of blood may be sampled safely (<500 μL), which limit the measure of several markers of health status and chemical residues. Here, we documented the partitioning of Cd and Pb in the blood of European Blackbirds Turdus merula in order to propose usable relationships between whole blood concentrations (for which toxicological benchmarks exist) and those measured in the erythrocytes. Sixty-two blackbirds were trapped along a pollution gradient (smelter of Metaleurop Nord, Northern France). Blood was sampled and Cd and Pb concentrations were measured both in whole blood and in the erythrocytes only. Birds coming from the most contaminated sites exhibited high residues for both Cd and Pb. We assessed that 73% and 99% of Cd and Pb, respectively, were associated to erythrocytes. Strong linear relationships, that were not influenced by neither the age nor the sex, were established between whole blood residues and those of erythrocytes for Cd and Pb (adj-R² = 0.78 and 0.93, respectively). Present findings are promising to optimize the use of small blood samples in order to investigate several responses relative to wildlife health status.     

Effects of experimental acidification on mobilisation of metals from sediments of limed and non-limed lakes

In order to study the influence of pH on the mobilisation of metals from lake sediments, intact sediment cores with overlying water were sampled from one lime treated lake and one acidified lake. The overlying water of two cores from each lake was successively acidified to pH 4.2 over a period of 3 months. In the acid treated samples from the limed lake, the initial concentrations of Al, Cd, Mn, Pb and Zn in the overlying water were generally lower and the final concentrations were higher than in the acid treated samples from the acidified lake. The labile inorganic fraction of Al (Al(i)) was increasingly dominating as pH decreased. Redox potential and pH in the sediment indicated that the upper two centimetres were involved in the exchange reactions. The experiment showed that mobilisation of metals from sediments can occur and the results indicated that mobilisation could contribute to increased concentrations of metals in lake water during reacidification of formerly lime treated lakes.     

Influence of glyphosate and its formulation (Roundup) on the toxicity and bioavailability of metals to Ceriodaphnia dubia

This study examined the toxicological interaction between glyphosate (or its formulation, Roundup) and several heavy metals to a freshwater cladoceran, Ceriodaphnia dubia. We demonstrated that all binary combinations of Roundup and metals (Cd, Cu, Cr, Ni, Pb, Se and Zn) exhibited "less than additive" mixture toxicity, with 48-h LC50 toxic unit > 1. Addition of glyphosate alone could significantly reduce the acute toxicity of Ag, Cd, Cr, Cu, Ni, Pb and Zn (but not Hg and Se). The ratio between glyphosate and metal ions was important in determining the mitigation of metal toxicity by glyphosate. A bioaccumulation study showed that in the presence of glyphosate the uptake of some metals (e.g. Ag) was halted but that of others (e.g. Hg) was increased significantly. Therefore, our study strongly suggests that glyphosate and its commercial formulations can control the toxicity as well as the bioavailability of heavy metals in aquatic ecosystems where both groups of chemicals can co-occur.     

Octanol-solubility of dissolved and particulate trace metals in contaminated rivers: implications for metal reactivity and availability

The lipid-like, amphiphilic solvent, n-octanol, has been used to determine a hydrophobic fraction of dissolved and particulate trace metals (Al, Cd, Co, Cu, Mn, Ni, Pb, Zn) in contaminated rivers. In a sample from the River Clyde, southwest Scotland, octanol-solubility was detected for all dissolved metals except Co, with conditional octanol-water partition coefficients, D(ow), ranging from about 0.2 (Al and Cu) to 1.25 (Pb). In a sample taken from the River Mersey, northwest England, octanol-solubility was detected for dissolved Al and Pb, but only after sample aliquots had been spiked with individual ionic metal standards and equilibrated. Spiking of the River Clyde sample revealed competition among different metals for hydrophobic ligands. Metal displacement from hydrophobic complexes was generally most significant following the addition of ionic Al or Pb, although the addition of either of these metals had little effect on the octanol-solubility of the other. In both river water samples hydrophobic metals were detected on the suspended particles retained by filtration following their extraction in n-octanol. In general, particulate Cu and Zn (up to 40%) were most available, and Al, Co and Pb most resistant (<1%) to octanol extraction. Distribution coefficients defining the concentration ratio of octanol-soluble particle-bound metal to octanol-soluble dissolved metal were in the range 10(3.3)-10(5.3)mlg(-1). The presence of hydrophobic dissolved and particulate metal species has implications for our understanding of the biogeochemical behaviour of metals in aquatic environments. Specifically, such species are predicted to exhibit characteristics of non-polar organic contaminants, including the potential to penetrate the lipid bilayer. Current strategies for assessing the bioavailability and toxicity of dissolved and particulate trace metals in natural waters may, therefore, require revision.     

Distribution of elements in needles of Pinus massoniana (Lamb.) was uneven and affected by needle age

Macronutrients (P, S, K, Na, Mg, Ca), heavy metals (Fe, Zn, Mn, Cu, Pb, Cr, Ni, Cd) and Al concentrations as well as values of Ca/Al in the tip, middle, base sections and sheaths of current year and previous year needles of Pinus massoniana from Xiqiao Mountain were analyzed and the distribution patterns of those elements were compared. The results indicated that many elements were unevenly distributed among the different components of needles. Possible deficiency of P, K, Ca, Mn and Al toxicity occurred in needles under air pollution. Heavy metals may threaten the health of Masson pine. Needle sheaths were good places to look for particulate pollutants, in this case including Fe, Cu, Zn, Pb, Cr, Cd and Al.     

Distribution of elements in needles of Pinus massoniana (Lamb.) was uneven and affected by needle age

Macronutrients (P, S, K, Na, Mg, Ca), heavy metals (Fe, Zn, Mn, Cu, Pb, Cr, Ni, Cd,) and Al concentrations as well as values of Ca/Al in the tip, middle and base sections, and sheaths of current year and previous year needles of Pinus massoniana from Xiqiao Mountain were analyzed and the distribution patterns of those elements were compared. The results indicated that many elements were unevenly distributed among the different components of needles. Possible deficiency of P, K, Ca, Mn and Al toxicity occurred in needles under air pollution. Heavy metals may threaten the health of Masson pine. Needle sheaths were good places to look for particulate pollutants, in this case including Fe, Cu, Zn, Pb, Cr, Cd and Al.     

Heavy metal and Pb isotopic compositions of aquatic organisms in the Pearl River Estuary, South China

The accumulation of trace metals in aquatic organisms may lead to serious health problems through the food chain. The present research project aims to study the accumulation and potential sources of trace metals in aquatic organisms of the Pearl River Estuary (PRE). Four groups of aquatic organisms, including fish, crab, shrimp, and shellfish, were collected in the PRE for trace metal and Pb isotopic analyses. The trace metal concentrations in the aquatic organism samples ranged from 0.01 to 2.10 mg/kg Cd, 0.02 to 4.33 mg/kg Co, 0.08 to 4.27 mg/kg Cr, 0.15 to 77.8 mg/kg Cu, 0.17 to 31.0 mg/kg Ni, 0.04 to 30.7 mg/kg Pb, and 8.78 to 86.3 mg/kg Zn (wet weight). High concentrations of Cd were found in crab, shrimp and shellfish samples, while high concentration of Pb was found in fish. In comparison with the baseline reference values in other parts of the world, fish in the PRE had the highest elevated trace metals. The results of Pb isotopic compositions indicated that the bioaccumulation of Pb in fish come from a wide variety of food sources and/or exposure pathways, particularly the anthropogenic inputs.     

Metal accumulation by wood-decaying fungi

Metal concentrations (Na, K, Rb, Mg, Ca, Sr, Mn, Fe, Cu, Zn, Cd, Al, and Pb) in the sporophores of ten wood-decaying macromycete species were related to concentrations in the wood substrates. Manganese, Sr, Ca, and Pb were usually excluded by the fungi, K, Rb, and, to a lower degree, Cd, Fe, Zn, Cu, Mg and Na, were accumulated. Accumulation ratios are compared with similar ratios for soil and litter inhabiting species previously studied.     

Trace metal accumulation and fish pathologies in areas affected by mining and metallurgical enterprises in the Kola Region, Russia

Throughout the Kola region of Russia there has been a substantial increase of metal concentrations in water, which are related to local discharges from metallurgical and mining industry, transboundary transmissions as well as indirect leaching of elements by acid precipitation. This study presents data on the levels of Ni, Cu, Sr, Al, Zn, Co, Mn, Pb, Cd, Hg in the organs and tissues of fish, and evaluates relationships with water chemistry. Special attention is paid to fish pathologies, whose aetiology is related to the accumulation of metals and the associated changes of the elementary ratios within the organism. Ecotoxicological assessment of the copper nickel, strontium and acidification regimes also is considered in this article. In general we observed a large number of lakes that are heavily contaminated by Ni and Cu. Fish in these lakes contain high concentrations of Ni and Cu and display frequent pathologies, mostly associated with the kidneys. In lakes contaminated with Sr, there also are high Sr levels in fish and pathologies associated with skeletal tissues. Exposure to acidified water appears to increase the transport of metals (including Al, Ni and Cu) into fish and hence the toxic effects.     

Bioavailability evaluation,uptake of heavy metals and potential health risks via dietary exposure in urban-industrial areas

A verity of human activities i.e. urbanization and industrialization have been resulted serious environmental contaminations by heavy metals in all over the world. The settlement of populations in urban and nearby industrial areas for economic development has significant share in their exposure to these metallic contaminants. Depending on the nature and type of the pollutants, targeted urban-industrial environments can have harmful and chronic health risk impacts on exposed local inhabitants and may require detoxification, healing and remedial therapy. Consequently, environmental monitoring as well as human health risk assessments of urban environments under industrial influence are key dominant features. We believe this work will provide new insights into the studies of metals exposure and associated health risks in emerging industrials cities of developing countries. Present study aimed to study the bioavailability of metals, quantify the changeability in soil and vegetable metal concentrations and estimation of human health risks via dietary exposure, focusing on urban-industrial environment. Soil and vegetable samples were collected in six random sites within the urban, periurban and industrial areas and analyzed for metal concentrations. In addition, risk assessment model proposed by US-EPA was employed to estimate the potential health risk of heavy metals via dietary intake. Results indicated that the heavy metal concentrations were noteworthy in periurban and urban-industrial areas. However, contamination levels varied with the type of vegetable, and the point source pollution such as traffic, urban wastes and industrial effluent. According to the estimated THQ and HI values for non-carcinogenic risk, little or no negative impact of heavy metals was observed on local inhabitants. However, the concentrations of Cr, Cd, Pb and Ni were nearly closed to the permissible limits described by US-EPA in urban-industrial areas. Conclusively, some efficient remedial strategies should be focus to overcome the increasing levels of Cr, Cd, Pb and Ni in this study area to protect the health of local inhabitants.     

Factors affecting trace-metal bioaccumulation in Finnish headwater lakes

Fourteen unpolluted Finnish headwater lakes with pH values varying from 4.8 to 7.0 were studied for trace-metal concentrations in water, sediment, aquatic plants (Nuphar luteum L., Sparganium sp.), aquatic insect larvae (Limnophilus sp., Phryganea sp.) and fish (Esox lucius L., Perca fluviatilis L., Coregonus sp., Salvelinus fontinalis L., Salmo trutta L.). Trace-metal deposition was estimated by analysing the snowpack. Non-parametric correlation analysis was carried out between trace metal concentrations in biota and pH, ANC, TOC, CA + Mg concentration in water and a given metal concentration in water and sediment. Bioaccumulation of several trace metals increased with increasing acidity and decreasing ANC in water. This was especially true for Pb and Cd. Aquatic plants were, in general, the best indicator group concerning differences in trace-metal bioaccumulation in lakes with different acidity. There was some evidence that a higher concentration of TOC in water may reduce bioaccumulation of Pb, Cd and Zn in aquatic plants and fish. The copper concentration in sediment was the only background variable explaining Cu concentration in aquatic insects. Multivariate analysis of the whole background data gave comparable preliminary results. Over 80% of the trace metal concentrations in biota of different lakes was explained by the background variables. In general, elevated concentrations of most of these trace metals can be expected to occur in the biota of acidified low calcareous lakes.     

Sequential sorption of lead and cadmium in three tropical soils

It is important to examine mechanisms of Pb and Cd sorption in soils to understand their bioavailability. The ability of three tropical soils to retain Pb, Cd, and Ca was evaluated. The objectives of this study were to (1) determine the extent to which soil sorption sites are metal specific, (2) investigate the nature of reactions between metals and soil surfaces, and (3) identify how metals compete for sorption sites when they are introduced to soils sequentially or concurrently. Lead was shown to be much less exchangeable than Cd and inhibited Cd sorption. Cadmium had little effect on Pb sorption, though both Ca and Cd inhibited the adsorption of Pb at exchange sites. Lead appears to more readily undergo inner-sphere surface complexation with soil surface functional groups than either Cd or Ca. Thus, regardless of when Pb is introduced to a soil, it should be less labile than Cd.     

Cadmium- and calcium-mediated toxicity in rainbow trout (Oncorhynchus mykiss) in vivo: interactions on fitness and mitochondrial endpoints

Rainbow trout were exposed to sublethal waterborne Cd (5 and 10 μg L⁻¹) and dietary Ca (60 mg g⁻¹), individually and in combination, for 30 d to elucidate the interactive effects and evaluate the toxicological significance of mitochondrial responses to these cations in vivo. Indices of fish condition and mortality were measured and livers, centers of metabolic homeostasis, were harvested to assess mitochondrial function and cation accumulation. All indices of condition assessed (body weight, hepatosomatic index and condition factor) were reduced in all the treatment groups. Mortality occurred in the Cd-exposed groups with dietary Ca partly protecting against and enhancing it in the lower and higher Cd exposure, respectively. State 3 mitochondrial respiration was inhibited by 30%, 35% and 40% in livers of fish exposed to Ca, Cd and Cd + Ca, respectively, suggesting reduced ATP turnover and/or impaired substrate oxidation. While the phosphorylation efficiency was unaffected, state 4 and state 4+ (+ oligomycin) respirations were inhibited by all the exposures. Mitochondrial coupling was reduced and transiently restored denoting partially effective compensatory mechanisms to counteract Cd/Ca toxicity. The respiratory dysfunction was associated with accumulation of both Cd and Ca in the mitochondria. Although fish that survived acute effects of Cd and Ca exposure apparently made adjustments to energy generation such that liver mitochondria functioned more efficiently albeit at reduced capacity, reduced fitness was persistent possibly due to increased demands for maintenance and defense against toxicity. Overall, interactions between Cd and Ca on condition indices and mitochondrial responses were competitive or cooperative depending on exposure concentrations and duration.     

Trace Element Inputs from a Coal Burning Power Plant to Adjacent Terrestrial and Aquatic Environments

Inputs of trace elements derived from coal ash to terrestrial and aquatic environments were investigated near an 83 MW coal-burning power plant. Comparisons were made between terrestrial inputs of trace elements through aerial deposition during 23 years before installation of electrostatic precipitators and aquatic inputs from ash disposal basins after installation. A gaussian plume model was used to predict deposition patterns of 29 trace elements in coal ash about the power plant. Detectable increases of only Sr, As, Sb, and Be in surface soils within 3 km of the power plant were predicted. Concentrations measured in surface soils were largely consistent with these predictions. Measurements of aerial deposition of Cd, Pb, Cu, and Mn at a site 5.5 km distant were similar to those in other rural areas and indicated that little of the measured Cd, Cu, Mn, or Pb was derived from fly ash. Concentrations of 12 heavy metals in effluents from the basin receiving ash were comparable to those predicted in rainfall deposited nearest the plant. It is concluded that at other coal combustion facilities, basin disposal could be a more serious contamination threat to aquatic environments than aerial dispersal of ash.