Assimilation efficiencies of Cd and Zn in the common carp (Cyprinus carpio): effects of metal concentration, temperature and prey type

The impact of several factors on the assimilation efficiency (AE) of Cd and Zn from food in the common carp (Cyprinus carpio) was studied. Tested prey species were midge larvae (Chironomus riparius), zebra mussels (Dreissena polymorpha) and oligochaetes (Tubifex tubifex). The Cd load of the larvae did not affect the Cd AE in the carp. The Zn AE however, was negatively related to the Zn load of the prey. Food quantity and starvation of the carp did not significantly affect the Cd AE. For Zn, a significant decrease in AE was found when carp were fed ad libitum. Decreasing the temperature from 25 degrees C to 15 degrees C did not influence the Cd AE, while for Zn a significant decrease of the AE was measured. Carp assimilated Cd from both zebra mussels and oligochaetes with a significantly lower efficiency in comparison to the midge larvae, although Zn AEs was prey independent.     

The influence of metal speciation on the bioavailability and sub-cellular distribution of cadmium to the terrestrial isopod, Porcellio dilatatus

Cadmium is a non-essential toxic metal that is able to bioaccumulate in both flora fauna and has the potential to biomagnify in some food chains. However, the form in which cadmium is presented to consumers can alter the bioavailability and possibly the internal distribution of assimilated Cd. Previous studies in our laboratory highlighted differences in Cd assimilation among isopods when they were provided with a plant-based food with either Cd biologically incorporated into plant tissue or superficially amended with ionic Cd(2+). Cd is known for its high affinity for sulphur ligands in cysteine residues which form the basis for metal-binding proteins such as metallothionein. This study compares Cd assimilation efficiency (AE) in Porcellio dilatatus fed with food amended with either cadmium cysteinate or cadmium nitrate in an examination of the influence of Cd speciation on metal bioavailability followed by an examination of the sub-cellular distribution using a centrifugal fractionation protocol. As hypothesized the AE of Cd among isopods fed with Cd(NO(3))(2) (64%, SE=5%) was higher than AE for isopods fed with Cd(Cys)(2) (20%, SE=3%). The sub-cellular distribution also depended on the Cd species provided. Those isopods fed Cd(Cys)(2) allocated significantly more Cd to the cell debris and organelles fractions at the expense of allocation to metal-rich granules (MRG). The significance of the difference in sub-cellular distribution with regard to toxicity is discussed. This paper demonstrates that the assimilation and internal detoxification of Cd is dependent on the chemical form of Cd presented to the isopod.     

Selenium assimilation and loss by an insect predator and its relationship to Se subcellular partitioning in two prey types

Subcellular selenium (Se) distributions in the oligochaete Tubifex tubifex and in the insect Chironomus riparius did not vary with Se exposure duration, which was consistent with the observations that the duration of prey Se exposure had little influence on either Se assimilation or loss by a predatory insect (the alderfly Sialis velata). However, these two prey types differed in how Se was distributed in their cells. Overall, the predator assimilated a mean of 66% of the Se present in its prey, which was similar to the mean percentage of Se in prey cells (62%) that was theoretically available for uptake (that is, Se in the protein and organelle fractions). Likewise, data for cadmium, nickel and thallium suggest that predictions of trace element transfer between prey and predator are facilitated by considering the subcellular partitioning of these contaminants in prey cells.     

Palygorskite as a feasible amendment to stabilize heavy metal polluted soils

The sorption behaviour of palygorskite has been studied with respect to lead, copper, zinc and cadmium in order to consider its application to remediate soils polluted with these metals. The Langmuir model was found to describe well the sorption processes offering maximum sorption values of 37.2 mg/g for lead, 17.4 mg/g for copper, 7.11 mg/g for zinc and 5.83 mg/g for cadmium at pH 5-6. In addition the effect of palygorskite amendment in a highly polluted mining soil has been studied by means batch extractions and leaching column studies. The soluble metal concentrations as well as the readily-extractable metal concentrations were substantially decreased at any concentration of palygorskite applied to soil (1, 2, 4%), although the highest decrease is obtained at the 4% dose. The column studies also showed a high reduction in the metal leaching (50% for lead, 59% for copper, 52% for zinc and 66% for cadmium) when a palygorskite dose of 4% was applied.     

Solid phase microextraction of aminodinitrotoluenes in tissue

Tubifex tubifex metabolizes 2,4,6-trinitrotoluene (TNT) to 2-amino-4,6-dinitrotoluene (2ADNT) and 4-amino-2,6-dinitrotoluene (4ADNT). Elimination rates of metabolically-generated ADNTs are low compared to ADNTs absorbed directly from water, suggesting that metabolically-generated ADNTs may be bound or sequestered within tissue and therefore less available for elimination. A solid phase microextraction (SPME) technique was used to extract ADNTs from T. tubifex tissue to investigate the recalcitrance of metabolically-generated ADNTs. As SPME is a gentle, non-depletive, equilibrium sampling technique useful for measuring "available" organic compounds, we hypothesized that metabolically-generated ADNTs would be less extractable than absorbed ADNTs. T. tubifex were exposed to two scenarios to generate tissues containing absorbed ADNTs and metabolically-generated ADNTs. Tissue was then homogenized in a neutral buffer solution. Polyacrylate-coated (PA) SPME fibers were deployed and agitated in tissue homogenates to measure available ADNTs. Extractability of ADNTs from tissue containing metabolically-generated ADNTs was significantly less than expected: 50-60% based on the theoretical fiber-water partition ratio. Extractability of absorbed ADNTs was significantly higher (81-90%), and not significantly different than expected. The lower SPME extractability of metabolically-generated ADNTs may stem from the unavailability of metabolically-generated ADNTs sequestered in tissue or bound to tissue macromolecules during metabolism of TNT to ADNT. Tissue extractions using SPMEs may be able to estimate bound organic residues in tissue and serve to indicate the toxicological bioavailability of tissue-associated organic compounds.     

Bioavailability of zinc in runoff water from roofing materials

Corrosion and runoff from zinc-coated materials and outdoor structures is an important source for the dispersion of zinc in the environment. Being part of a large inter-disciplinary research project, this study presents the bioavailability of zinc in runoff water immediately after release from the surface of 15 different commercially available zinc-based materials exposed to the urban environment of Stockholm, Sweden. Runoff water was analysed chemically and evaluated for its possible environmental impact, using both a biosensor test with the bacteria Alcaligenes eutrophus (Biomet^®) and the conventional 72 h growth inhibition test with the green alga Raphidocelis subcapitata. Chemical speciation modelling revealed that most zinc (94.3–99.9%) was present as the free Zn ion, the most bioavailable speciation form. These findings were confirmed by the results of the biosensor test (Biomet^®) which indicated that all zinc was indeed bioavailable. Analysis of the ecotoxicity data also suggested that the observed toxic effects were due to the presence of Zn²⁺ ions. Finally, regression analysis showed that, for this type of runoff samples, the rapid screening biosensor was capable of predicting (a) the total amount of zinc present in the runoff samples (R² of 0.93–0.98; p<0.05) and (b) the observed 72 h-EbC₅₀s (R² of 0.69–0.97; p<0.05).     

Speciation and mobility of cadmium in straw and wood combustion fly ash

Two fly ashes from biomass combustion have been analysed regarding cadmium speciation and mobility. A fly ash from straw combustion contained 10 mg Cd/kg dry matter, and around 50% of the cadmium was leachable in water. The possible main speciation of cadmium in this fly ash was CdCl2. When adding this fly ash to agricultural soil a threat for groundwater contamination and plant uptake is existing. A fly ash from wood chip combustion had 28.6 mg Cd/kg dry matter. In this fly ash, the cadmium was bound more heavily, with only small amounts of cadmium leached in mild extractants. A possible speciation of cadmium in this fly ash was as oxide or as CdSiO3. Long-term effects and accumulation of cadmium could be a problem when adding this fly ash to agricultural or forest soils.     

水蚯蚓微生物共生系统的脱氮特性

采用泥水同步降解的"水蚯蚓-微生物共生系统",考察了该系统污泥减量能力以及污染物去除性能,研究了水蚯蚓对共生系统脱氮特性的影响。结果表明,与对照组相比,实验组污泥减量率为25.0%,污泥性状无明显差异。实验组氨氮与总氮去除率明显低于对照组,实验组每周期单位质量活性污泥氨氮与总氮去除质量分别为6.63 mg/g与5.81mg/g,均低于对照组。共生系统脱氮性能下降主要由水蚯蚓含氮物质释放引起,活性污泥本身硝化能力没有降低,反而略有提高,反硝化能力没有明显改变。"水蚯蚓-微生物共生系统"对中低氨氮浓度的废水处理具有较大的潜力。     

Use of oxygen consumption and ammonium excretion to evaluate the sublethal toxicity of cadmium and zinc on Litopenaeus schmitti (Burkenroad, 1936, Crustacea).

Penaeid shrimps are important resources for worldwide fisheries and aquaculture. In Brazil, Litopenaeus schmitti (L. schmitti) is a important commercially exploited species and is an ideal animal for studying the impairment caused by the effects of heavy metals that are often detected in coastal areas. The main purpose of the present study was to detect the acute toxicity of cadmium and zinc to L. schmitti and investigate their effects on oxygen consumption and ammonium excretion, investigations that have not been carried out in this species before. First, the acute toxicity of cadmium and zinc to L. schmitti 24, 48, 72, and 96-hour medium lethal concentration was examined, which resulted in the following values: 0.98, 0.54, 0.32, and 0.18 mg/L for cadmium and 1.64, 1.22, 0.86, and 0.31 mg/L for zinc. Furthermore, we also found that exposure of shrimp to cadmium and zinc caused an inhibition in oxygen consumption of 55.92 and 44.09%, respectively, relative to the control. However, after separate exposure to cadmium and zinc, elevations in ammonium excretion were obtained, which were 174.28 and 162.5% higher than the control, respectively.     

锌、铁等离子对氧化锌烟气脱硫工艺中亚硫酸锌氧化的影响

在氧化锌法脱除烟气SO2工艺中,脱硫产物亚硫酸锌的氧化是实现锌、硫资源回收的关键环节。在pH为4～5,25℃等条件下,考察了锌、铁、镉离子对亚硫酸锌氧化过程的影响。结果发现,铁离子对亚硫酸锌氧化过程有较强的催化作用,锌离子有一定的催化作用,而低浓度的镉离子几乎不影响氧化过程。进一步的研究表明,锌、铁离子的独自催化氧化速率对各自的浓度均为0．5级响应,但在混合状态下,锌离子对铁离子的催化过程有抑制作用。     

Speciation of zinc in contaminated soils

The chemical speciation of zinc in soil solutions is critical to the understanding of its bioavailability and potential toxic effects. We studied the speciation of Zn in soil solution extracts from 66 contaminated soils representative of a wide range of field conditions in both North America and Europe. Within this dataset, we evaluated the links among the dissolved concentrations of zinc and the speciation of Zn(2+), soil solution pH, total soil Zn, dissolved organic matter (DOM), soil organic matter (SOM) and the concentrations of different inorganic anions. The solid-liquid partitioning coefficient (K(d)) for Zn ranged from 17 to 13,100Lkg(-1) soil. The fraction of dissolved Zn bound to DOM varied from 60% to 98% and the soil solution free Zn(2+) varied from 40% to 60% of the labile Zn. Multiple regression equations to predict free Zn(2+), dissolved Zn and the solid-liquid partitioning of Zn are given for potential use in environmental fate modeling and risk assessment. The multiple regressions also highlight some of the most important soil properties controlling the solubility and chemical speciation of zinc in contaminated soils.     

Levels and interactions of heavy metals in sea birds from Svalbard and the Antarctic

Samples of liver and kidney from 92 seabirds of ten species collected on Spitsbergen and in the Antarctic, were analysed for their content of copper, zinc, cadmium, lead, mercury and selenium. Significantly higher levels of copper and zinc were observed in birds from Spitsbergen than in those from the Antarctic, while the opposite was true for selenium. The highest cadmium levels were found in fulmar Fulmarus glacialis and macaroni penguin Eudyptes chrysolophus. A possibility of kidney damage due to cadmium exists. The highest mercury levels were recorded in brown skua Catharacta lonnbergi collected at Bouvet?ya. Lead was not detected in any of the birds. Significant correlations were observed between levels of several of the metals studied, especially between cadminum and zinc and between mercury and selenium. However, for all birds, the highest correlation coefficients were observed when the molar concentrations of cadmium plus mercury, and selenium plus zinc, were used in the calculations. Thus several protective mechanisms may operate to diminish effects of heavy metal contaminants.     

Heavy metal binding by the polymeric organic fractions of sewage sludges

Organic complexes in sewage sludge play an important role in the speciation and transformation of metals into potentially more toxic and bioavailable forms. Two organic fractions, bacterial extracellular polymer and fulvic acid, were extracted from mixed liquor and digested sewage sludge by methods established as the most appropriate. The homogeneity of the extracts was verified using gel permeation chromatography. Conditional stability constants and complexation capacities of the organic fractions from the sludges with copper, cadmium, nickel and zinc have been determined using equilibrium dialysis titration. Organic fractions extracted from digested sludge demonstrated a greater capacity to complex metals over mixed liquor extracts. Copper formed stronger complexes than nickel with the mixed liquor biomass and cadmium exhibited the greatest affinity for digested sludge organic matter.     

The effects of cadmium or zinc multigenerational exposure on metal tolerance of Spodoptera exigua (Lepidoptera: Noctuidae)

The effects of ten generational zinc or cadmium pre-exposure on metal tolerance among beet armyworm Spodoptera exigua individuals were compared. These effects were assessed in animals from the 11th generation, reared on a diet either uncontaminated or contaminated with metal (cadmium or zinc). The survival rate of larvae and the degree of metal accumulation (in larvae, pupae and moths; among larval organs: gut and fat body) were analysed. Catalase, superoxide dismutase and glutathione transferase activity in larval organs of individuals subjected to different metal treatments were also measured. Animals transferred from control rearing to metals (cadmium or zinc) in the 11th generation, as well as those from multigenerational zinc treatment, but not from multigenerational cadmium treatment, had a significantly lower survival rate than control animals. Insects from the groups with the high metal treatment had high bioaccumulation factors (above 3.7 and 2.3 following cadmium and zinc, respectively). Cadmium (but not zinc) pre-exposure had a significant effect on metal accumulation in larvae. Multigenerational metal pre-exposure seemed to have mainly a negative effect on glutathione transferase activity in the gut of larvae from the 11th generation, in the case of the individuals exposed to metal other than that used in pre-exposure treatment or kept in control conditions. However, in the case of zinc pre-exposure, such effect was only apparent when zinc was replaced by cadmium. The long-term effect of cadmium on catalase activity in larvae was found.     

Computational spectroscopic study of copper, cadmium, lead and zinc interactions in the environment

Molecular modelling has been used to investigate the interactions of various heavy metals, in order to understand and possibly to control the nature and behaviour of metals, especially in the aquatic environment. The interactions of copper, cadmium, lead and zinc with organic acids were studied using density functional theory (DFT) calculations. Carboxylic acid was used as a model molecule. The structure of each metal carboxylate was optimized and the vibrational spectrum calculated. The results indicate that there is a shift in the calculated v_S(C=O) of metal carboxylates compared with that of carboxylic acid. It was also found that hexaaqua structures of both cadmium and zinc are stable whereas those of copper and lead are not. Furthermore, dipole moment calculations indicate that cadmium carboxylate dihydrate is more representative of cadmium interactions in the aquatic environment. Moreover, hexaaquo cadmium could further interact with surrounding molecules in the aquatic environment.     

Influence of titanium dioxide nanoparticles on speciation and bioavailability of arsenite

In this study, the influence of the co-existence of TiO₂ nanoparticles on the speciation of arsenite [As(III)] was studied by observing its adsorption and valence changing. Moreover, the influence of TiO₂ nanoparticles on the bioavailability of As(III) was examined by bioaccumulation test using carp (Cyprinus carpio). The results showed that TiO₂ nanoparticles have a significant adsorption capacity for As (III). Equilibrium was established within 30 min, with about 30% of the initial As (III) being adsorbed onto TiO₂ nanoparticles. Most of aqueous As (III) was oxidized to As(V) in the presence of TiO₂ nanoparticles under sunlight. The carp accumulated considerably more As in the presence of TiO₂ nanoparticles than in the absence of TiO₂ nanoparticles, and after 25-day exposure, As concentration in carp increased by 44%. Accumulation of As in viscera, gills and muscle of the carp was significantly enhanced by the presence of TiO₂ nanoparticles.     

Effects of pH on the toxicity of cadmium, copper, lead and zinc to Folsomia candida Willem, 1902 (Collembola) in a standard laboratory test system

EC₅₀s for cadmium, copper, lead and zinc were determined for juvenile production of Folsomia candida at pH6.0, 5.0 and 4.5 in a standard laboratory test system. In contrast to most previous studies where metal toxicity was increased at low pHs, in our experiments there was no clear relationship between soil acidity and EC_{50-reproduction} in this species. The EC_{50-reproduction} values (μg g⁻¹) for cadmium and zinc were similar at all three pHs (pH6.0: Cd 590, Zn 900; pH5.0: Cd 780, Zn 600; pH4.5: Cd 480, Zn 590). In contaminated field sites adjacent to primary zinc smelters, zinc is invariably present in soils at concentrations of at least 50 times that of cadmium Thus deleterious effects of mixtures of these metals on populations of Collembola in such sites can be attributed to zinc rather than cadmium.     

The influence of particle surface characteristics on pollutant metal uptake by cells

The phosphatic mineral, hydroxyapatite, and two ion exchange resins have been used as artificial sediment particles. The surface properties of these materials have been studied using the Langmuir adsorption isotherm to calculate the binding capacity (B(max)) and the adsorption constant (K(L)) for zinc and cadmium ions. Mussels (Mytilus edulis) were fed on the particles and their digestive glands were subsequently removed and subjected to cell fractionation. The supernatant fraction was used to determine cytosol metal levels as a measure of the materials absorbed from the ingested particles. The level of cytosol zinc and cadmium was correlated with the K(L) values of the artificial sediments. It is suggested that phagocytosis of sediment particles plays an important part in transferring pollutants into benthic organisms and that the efficiency of this process is related to the adsorption coefficient of the particle surfaces.     

Oribatid mite communities and metal bioaccumulation in oribatid species (Acari, Oribatida) along the heavy metal gradient in forest ecosystems

The responses of oribatid communities to heavy metal contamination were studied. Concentration of cadmium, copper and zinc in nine oribatid species along a gradient of heavy metal pollution was measured. Oribatid mites were sampled seasonally during two years in five forests located at different distances from the zinc smelter in the Olkusz District, southern Poland. The most numerous and diverse oribatid communities were found in the forest with moderate concentrations of heavy metals. Analysis by atomic absorption spectrophotometry revealed large differences in metal body burdens among species. All studied oribatid species appeared to be accumulators of copper with Oppiella nova, Nothrus silvestris and Adoristes ovatus characterized by the highest bioaccumulation factors. Most species poorly accumulate cadmium and zinc. The accumulation of heavy metals in the body of oribatids was not strictly determined by their body size or the trophic level at which they operate.     

Trade-offs between elimination and detoxification in rainbow trout and common bivalve molluscs exposed to metal stressors

The purpose of this paper was to examine trade-offs between elimination and detoxification in rainbow trout and three common bivalve molluscs (clam, oyster, and scallop) exposed to cadmium (Cd), copper (Cu), and zinc (Zn) based on recent reported experimental data. We incorporated metal influx threshold with subcellular partitioning to estimate rate constants of detoxification (k_d) and elimination (k₂). We found that the relationships between k₂ and k_d were negative for rainbow trout and positive for bivalve molluscs. However, the relationships between k_d and % metal in metabolically detoxified pool were found positive for rainbow trout and negative for bivalve molluscs. Our results also indicated that rainbow trout had higher accumulation (∼60-90%) in metabolically active pool when exposed to essential metals of Cu and Zn and had only 10-50% accumulation in response to non-essential metal of Cd. Based on a cluster analysis, this study indicated that similarity of physiological regulations among study species was found between Cd and Zn. Our study suggested that detoxification can be predicted by an elimination-detoxification scheme with the known elimination rate constant. We concluded that quantification of trade-offs between subcellular partitioning and detoxification provides valuable insights into the ecotoxicology of aquatic organisms and enhances our understanding of the subcellular biology of trace metals.