Determination of types of interactions exhibited by binary mixtures of heavy metals tested against the hermit crab,Clibanarius africanus

Single and joint action toxicity of heavy metal compounds (ZnCO₃, CuSO₄ and CdSO₄) were carried out against the hermit crab, Clibanarius africanus in laboratory bioassays. On the basis of 96?h LC₅₀ values, CuSO₄ (96?h LC₅₀?=?0.03?mM) was found to be the most toxic followed by CdSO₄ and ZnCO₃ (96?h LC₅₀?=?0.24?mM) in decreasing order of toxicity. The evaluation of the metal compounds in mixtures of ZnCO₃–CuSO₄, ZnCO₃–CdSO₄ and CdSO₄–CuSO₄ in pre-defined molar ratios revealed that interactions between Zn–Cu and Zn–Cd test mixtures were in conformity with the models of antagonism (reduction in toxicity of constituent metals). The synergistic ratios (S.R.s) and relationship between observed/predicted 96?h LC₅₀ values (relative toxic unit, RTU) were consistently below 1, indicating antagonistic interactions. Analysis using isobolograms also indicated the interactions between the mixture components to be antagonistic. However, with regards to CdSO₄–CuSO₄ test mixtures, the interactions between these metals were mainly in conformity with the model of synergism. The S.R. and RTU values were largely above 1, indicating synergistic interactions. The importance of the joint action evaluations for the management and protection of aquatic ecosystems, particularly in the setting up of water quality criteria was discussed.     

Hematoxicity and hepatoxicity attributed to zinc and cadmium in the Norwegian rat

This study was carried out to determine changes in the blood and liver of rats given oral doses of cadmium (Cd) and zinc (Zn). Thirty 3 month old rats were kept six to a compartment in a well-demarcated five compartment cage labeled A, B, C, D, and E. After 2 weeks of acclimatization, and with ad libitum administration of water and feed, group A and B rats were, respectively, exposed to 100 mg CdSO₄ and 2200 mg ZnSO₄, respectively, mixed with their feed. Group C rats were fed with a combination of 100 mg CdSO₄ and 2200 mg ZnSO₄ mixed with their feed, while group D rats were exposed to 100 mg CdSO₄ mixed with their feed for 48 h, and after they were given 2200 mg ZnSO₄ for 96 h. Group E rats served as control and were fed a normal diet. Analysis of blood samples after 5 days showed that in rats of groups A, B, C, and D, WBC count increased from 6800 to 12,400 mm^?3 and platelets from 26,000 to 88,000 mm^?3. Reduction in blood counts were found for RBC from 13.8 to 4.7 × 10⁶ mm^?3, hemoglobin from 15.6 to 11.4 dL^?1, and PCV from 47 to 34%. ESR was the same 1.0 mm h^?1 in all groups. Severe damage to the liver was also shown by severe degeneration of hepatocytes and increase in Kuppfer cells. The above observations were mildest in the liver of group C rats. A reduction of body weight was observed in all treatment groups. Cd and Zn were found to be hematoxic and hepatotoxic in the Norwegian rat with Cd exhibiting greater toxicity than Zn. Toxicity of Cd was suppressed by Zn only when both metals were admistered at the same time, but a delay in intake of Zn (after 48 h) had little effect on Cd toxicity.     

Low level inhalation experiments with four different cadmium compounds in rats†

This long‐term inhalation study was designed to describe the toxicity and the carcinogenic risk from Cd compounds because it had been shown from former long‐term inhalation studies that cadmium choloride induced primary lung tumors in Wistar rats. It was therefore logical to examine whether other cadmium compounds to which human beings are more frequently exposed have also carcinogenic potency. In a long‐term inhalation study cadmium aerosols consisting of cadmium chloride (CdCl₂), cadmium oxide (CdO) as dusts and fumes, cadmium sulfate (CdSO₄), cadmium sulfide (CdS) and a combination of cadmium oxide/zinc oxide were used. Wistar rats were continuously exposed in inhalation chambers for 18 months 22 hrs a day or for 40 hrs a week. The studies will be terminated at the mean survival life time of the species. The aerosols were generated by several different systems. The particles of the cadmium aerosols have the average mass medium diameters in the range from 0.2 to 0.5 μm.     

Synergistic effects of salinity,temperature and heavy metals on mortality and osmoregulation in marine and estuarine isopods (Crustacea)

The effects of cadmium (3CdSO₄·8H₂O), zinc (ZnSO₄·7H₂O) and lead [Pb (NO₃)₂] on mortality, and cadmium, zinc and mercury (HgCl₂) on osmoregulation, have been recorded for marine and estuarine species of isopods (Crustacea). The marine species studied were Idotea baltica, I. neglecta, I. emarginata and Eurydice pulchra, which were adapted to 100, 80, 60 and 40% sea water (SW) (100% SW э 34‰ S). The estuarine species used were Jaera albifrons sensu stricto and J. nordmanni, which were adapted to 100, 50, 10 and 1% SW. Both groups of isopods have low mortalities in 100% SW with 10 and 20 ppm of cadmium, zinc and lead, but a decrease in salinity caused an increase in the toxicities of these metals and reduced the LT₅₀ values (time, in hours, to 50% mortality). Mortalities at 10°C were generally higher than those recorded at 5°C. Cadmium had no significant effect on the osmoregulation of I. baltica and I. emarginata in 100 and 80% SW at 5°C, but this metal significantly lowered the blood osmotic concentration of I. neglecta in 80% SW. Zinc did not alter the haemolymph osmotic concentration of I. neglecta in 100 and 80% SW, but significantly lowered the blood osmotic concentration of I. baltica in 100% SW. Cadmium, zinc and mercury also significantly altered the osmoregulatory ability of J. albifrons in dilute saline.     

Metal-free oxidation of aldehydes to acids using the 4Na<Subscript>2</Subscript>SO<Subscript>4</Subscript>·2H<Subscript>2</Subscript>O<Subscript>2</Subscript>·NaCl adduct

Oxidation of aldehydes to carboxylic acids is a major reaction. Conventionally, this reaction is carried out with oxidants and metal catalysts, thus producing unwanted metal waste. Recently, aqueous media have been used as an alternative for toxic organic solvents. Here, we tested the clathrate-structured, neutral hydrogen peroxide adduct 4Na₂SO₄·2H₂O₂·NaCl for the oxidation of aldehydes to acids in aqueous solution. We found that various aromatic, heteroaromatic and aliphatic aldehydes were selectively oxidized to corresponding acids in 70–98% yields. This simple acid–base treatment allows to separate easily the acid product in high purity without any organic solvent. Moreover, the adduct is produced using 25% H₂O₂, with inexpensive sodium sulphate, Na₂SO₄, and sodium chloride, NaCl. The adduct is a non-toxic white crystalline solid, readily soluble in water, and easy to handle.     

Niedere pilze als testorganismen für schadstoffe in meer- und brackwasser die wirkung von schwermetallverbindungen und phenol auf Thraustochytrium striatum

Three test-series were applied, which differed in regard to the basal medium (natural or artificial sea water, salinity level, addition of detergent); the culture conditions (primary cultures, subcultures, back-inoculations into basal medium without toxic metals); the criterion employed (zoospore activity, sporangia development, or dry weight of Thraustochytrium striatum Schneider). The temperature applied was 18° to 20°C. The sea water-pollen-method (MWP) proved to be the most suitable: it is simple and more sensitive than the other tests; subcultures and back-inoculations are possible without much additional work; conditions simulate nature; first results are available after 3 to 4 days. The SMS-method (enriched natural sea water of different salinities) provides additional information on salinity effects. Nine substances have been tested: (CH₃COO)₃Hg, HgCl₂, CdCl₂·H₂O, ZnSO₄ ·7H₂O, NiSO₄·7H₂O, CuSO₄·5H₂O, CoCl₂·6H₂O, MnCl₂ ·4H₂O, and phenol. In regard to their toxicity these substances can be divided into 2 groups: Hg- and Cd-salts inhibit development down to greater dilutions than the remainder; Zn and Ni seem to yield intermediate effects. Salinity modifies the toxic effects of the test substances. In higher salinities, comparable concentrations of test substances reveal stronger inhibitory effects than in lower salinities. Detergents may augment the toxic effects, at least of CuSO₄. The marine lower fungus T. striatum is a useful organism for testing biological consequences of water pollutants.     

Cadmium accumulation in the female shore crab Carcinus maenas during the moult cycle and ovarian maturation

 The influence of moulting and ovarian maturation on cadmium accumulation in the tissues of female shore crabs Carcinus maenas exposed to 1 mg Cd l⁻¹ in the water was investigated. Cadmium accumulation in all tissues examined was markedly increased in crabs in the postmoult stages (A and B) compared to crabs in all other moult stages. During the moult cycle, average cadmium accumulation in the midgut gland ranged from 29 μg Cd g⁻¹ dw at premoult stage (D₂) to 589 μg Cd g⁻¹ dw at postmoult stage (A). Average cadmium concentrations in the haemolymph ranged from 0.56 μg Cd ml⁻¹ at intermoult stage (C₄) to 4.6 μg Cd ml⁻¹ at postmoult stage (A), while the gills accumulated from 103 μg Cd g⁻¹ dw in intermoult stage (C₃) to 352 μg Cd g⁻¹ dw in postmoult stage (A). Cadmium concentration in gills and haemolymph was also significantly higher in crabs in late premoult stage (D₃) compared to C₄-crabs, while midgut gland cadmium concentration remained elevated in C₁- and C₃- intermoult stages relative to C₄. During ovarian maturation the cadmium accumulation in midgut gland, gills, ovaries and haemolymph decreased. Average cadmium concentration in the midgut gland decreased from 63 μg g⁻¹ dw in ovarian Stage I to 19 μg g⁻¹ dw in ovarian Stage VI. The same pattern was observed for gills, haemolymph and ovaries. The present study demonstrates that cadmium accumulation in the female shore crab strongly depends on the physiological status of the animal. A possible association between physiological calcium requirements and cadmium accumulation during moulting is discussed. Received: 20 January 2000 / Accepted: 20 July 2000     

Lead- and cadmium-induced histopathological changes in gill,kidney and liver tissue of freshwater climbing perch Anabas testudineus (Bloch, 1792)

The objective of this study was to examine the toxicological effect of two major heavy metal pollutants, lead chloride (PbCl₂) and cadmium chloride (CdCl₂), in the freshwater climbing perch, Anabas testudineus. Fish were exposed to 1.0 and 2.0 mg/L both metals and histopathological changes in gill, kidney and liver tissues were studied. Major changes observed in gill tissue were epithelial lifting, proliferation of epithelial cells, fusion of secondary lamellae, hyperplasia and hypertrophy of mucous cells, and necrosis of epithelial cells. Cell necrosis, degenerated kidney tubules, congestion, lymphocytic infiltration and vacuolation were the major abnormalities observed in kidney tissue. The most conspicuous changes in liver were darker nucleoli, irregularly shaped hepatocytes with dilated blood capillaries, and focal as well as single necrosis. Fish specimens exposed to PbCl₂ exhibited pronounced changes in all tissues examined compared with those exposed to CdCl₂. It is evident from this study that heavy metals can cause significant histopathological changes in fish tissue.     

Gradient ion chromatography of environmentally relevant anions in scrubbers of waste incinerators

Improved separations of a wide range of anions of environmental importance in scrubbers of waste incinerators were achieved by applying a Na₂B₄O₇/NaOH composition gradient of low electrical conductivity in combination with suppressed ion chromatography. Fluoride, Acetate, Formiate and 16 other ions including Iodide could be separated within the same run in less than 20 minutes. The selective detection of small amounts of several anions in presence of excessive amounts of Chloride and Sulfate is discussed. Furtheron various adsorbents were tested for the removal of Phenol as a potential trouble shooting source in 5 ion chromatography. Depending on the analytical task and circumstances several adsorbents reveiled promising properties.     

Uptake and cellular distribution of cadmium in Mytilus edulis

Cadmium uptake has been studied in starved and fed Mytilus edulis L. It is suggested that fairly elevated cadmium contents in fed mussels are not due to contaminated food, but to increased pumping rate when food is available. Highest concentration and main body burden are found in the mid-gut gland. Transport via haemolymph, and selective discrimination at the basement lamina of the mid-gut gland tubuli are regarded as mainly responsible for accumulation. Mercury seems to be processed in a similar way as cadmium. In the tubuli, both metals are immobilized in membrane-bound vesicles, which are finally defaecated.This work was financially supported by the German Research Council (DFG) (Sto 75/4 and Th 158/13).     

Heavy-metal adsorption by non-living biomass

The adsorption of some heavy metals onto the walls of harvested, washed, and dried non-living biomass cells of different Pseudomonas strains was studied at optimum experimental conditions using a simplified single component system. The Langmuir adsorption model was found to be a suitable approach to describe the system via multi-step processes. Isotherms measured at 30.0°C and pH 5.5 with [M]_total?=?10–100 mM for tight, reversible Cr⁶⁺(aq), Ni²⁺(aq), Cu²⁺(aq) and Cd²⁺(aq) binding by the cell walls of the investigated biomass fit the Langmuir model and give the pH-independent stoichiometric site capacities ν _i and equilibrium constants K _i for metal binding at specific biomass sites i?=?A, B, C, and D. Tight binding sites A, B, and D of the non-living biomass are occupied by Cr^VI, sites A and C by Ni^II, sites A and D by Cd^II, and only site B by Cu^II. It is concluded that ν _i is a stoichiometric parameter that is independent of the magnitude of K _i for binding site i and that the studied heavy metals selectively and tightly bind at different biomass sites.     

Metabolic responses in zebrafish (Danio rerio) exposed to zinc and cadmium by nuclear magnetic resonance -based metabolomics

Heavy metals are common marine and soil pollutants that are mainly the result of industrial activity, and are a threat to the environment and human health. In this study, ¹H nuclear magnetic resonance (NMR)-based metabolomics was applied to adult Danio rerio to monitor the metabolic change as a response to ZnCl₂ and CdCl₂ exposure at different concentrations for 72?h. NMR spectroscopy was used to identify and quantify the metabolites extracted from D. rerio. The metabolite profiles of the control and heavy metal exposed group were classified by partial least squares – discriminant analysis (PLS-DA) analysis, and potential contaminant-specific biomarkers were suggested. For the ZnCl₂-exposed zebrafish, the levels of ATP, aspartate and NAD⁺ were increased, whereas the levels of formate, inosine, hypoxanthine and succinate decreased. In addition, the CdCl₂-exposed zebrafish showed an increase in the levels of ATP and formate and a decrease in the levels of glutamate, inosine and glutathione. Overall, Zn and Cd may lead to neurotoxicity, disturbances in the energy metabolism and oxidative stress. Our finding demonstrated that the application of NMR-based metabolomics might be useful for detecting the toxicity caused by sub-lethal concentrations of heavy metal contaminants in the environment.     

Evidence for a new mechanism of Fe2O3 decomposition in lightweight aggregate formation

Hematite (Fe₂O₃) chemical reduction into FeO and Fe₃O₄ by releasing O₂ at high temperatures is considered one of the generally accepted mechanisms for processing waste minerals and clay into lightweight aggregate construction materials. In many case studies, this mechanism has not been strictly confirmed. To verify whether hematite can effectively release O₂ at 1,000–1,260°C, a material containing hematite, simulating waste sediments from a Taiwanese reservoir, was shaped into pellets and fired into lightweight aggregates at high temperatures for 20 min and studied with various techniques. As revealed by the X-ray absorption near-edge structure technique, almost all the hematite remained as Fe(III) in the pellets when fired at 1,000–1,260°C, implying a negligible release of O₂ leading to the creation of pores. This finding shows that the generally accepted mechanism for lightweight aggregate formation associated with hematite decomposition into FeO, Fe₃O₄, and O₂ is invalid. Furthermore, Fe(III)-containing composites were formed in the fired pellets. Although firing at 1,000°C can trigger the decomposition of the components K₂CO₃, Na₂CO₃, and CaCO₃ with a release of CO₂, the sintering reaction was seemingly too weak to encapsulate the gases effectively. For pellets fired at 1,050–1,150°C, pores grew in size because the sintering reaction sufficed to generate a glassy phase that could better encapsulate gases.     

Induction of gene mutations in salmonella and Drosophila by soluble Cr(Vi) compounds: Synergistic effects of nitrilotriacetic acid

The interaction between NTA and soluble Cr(VI) (K₂Cr₂O₇) was studied by the Ames test on S. typhimurium and the sex‐linked recessive lethal test on D. melanogaster. In both systems a synergistic effect of NTA on Cr(VI) mutagenicity took place at sub‐toxic doses of Cr(VI). The synergism could depend on the action of NTA on intracellular Cr(VI) reduction, as more Cr(VI) was reduced in vitro to Cr(III) by Salmonella and Drosophila protein extracts in the presence of NTA. A similar enhancement of soluble Cr(VI) mutagenicity was produced by low doses of EDTA.     

Patterns of trace-metal distribution in tissues of Pleoticus muelleri (Crustacea: Decapoda: Solenoceridae)

Trace-metal distribution in tissues of the shrimp Pleoticus muelleri Bate from the Patagonian region, Argentina, was related to sex, size and physiological condition. Concentrations of cadmium, copper, manganese and zinc were determined in the digestive gland, male reproductive system and muscle of adult specimens. Significant (p<0.01) sex-dependent differences in mean metal concentrations (g g^-1 wet wt) were found in the following tissues of males and females, respectively: digestive gland, Cu, 82.9 and 30.8; Zn, 32.5 and 44.9; reproductive system, Zn, 12.8 and 38.6; Mn, 1.7 and 3.1; Cd, 0.29 and 0.58. Metal levels of muscle showed no significant differences between sexes. Cadmium was not detected in muscle, suggesting that its incorporation into this tissue was strictly regulated. Metal concentrations in the male reproductive system were in general weakly correlated (0.001<p<0.05) with either body size or the concentration of metals in the digestive gland. The developing ovary incorporated substantial amounts of zinc, while cadmium and copper levels decreased at proportional rates (p<0.001). The patterns of the variations in the concentrations of these metals in the ovary strongly suggested that a regulatory mechanism operated throughout oogenesis. Manganese was not involved in this presumptive mechanism. The results of this study are discussed in terms of concentrations and in absolute amounts for standardized individuals.     

Comparative study between using natural and synthetic zeolites for the improvement of soil salinity and crop yield

The effects of natural zeolite (clinoptilolite, NZ) and synthetic zeolite (Y, SZ) on salinity and the presence of the harmful salts in the soil were compared on Raphanus sativus L. Nine soil treatments were studied: 1 (control), 2 (NaCl), 3 (Na₂SO₄), 4 (NZ), 5 (SZ), 6 (NZ?+?NaCl), 7 (SZ?+?NaCl), 8 (NZ?+?Na₂SO₄), and 9 (SZ?+?Na₂SO₄). Five radish seeds were planted in each pot. Each treatment was repeated 10 times. After 50 days under equal conditions some parameters consisting of the number of leaves (NL), total leaf area (TLA), total fresh weight (TFW), total dry weight (TDW), root fresh weight (RFW), air fresh weight (AFW), root dry weight (RDW) and air dry weight (ADW) were determined. Results showed that adding either NZ or SZ to salinic soil (treatments NZNaCl, NZNa₂SO₄, SZNaCl and SZNa₂SO₄) increased AFW, TFW and TDW. Using both NZ and SZ in normal soil increased the weight of plants by developing AFW. Further NZ was more effective on soil with NaCl than SZ.     

Effects of cadmium on intracellular cation homoeostasis in the yeast Saccharomyces cerevisiae

Previous studies have demonstrated that cadmium can induce biochemical and physiological changes in yeast Saccharomyces cerevisiae. However, studies on the influence of cadmium on the ion balance in the cell and the interaction between cadmium and other ions are still relatively few in number. By using inductively coupled plasma-atomic emission spectrometry, the contents of some cations, including Zn²⁺, Ca²⁺, Fe³⁺, Cu²⁺, Mg²⁺, K⁺, and Na⁺ were measured. The data showed that the levels of Zn²⁺ and Fe³⁺ were increased, while those of Cu²⁺, K⁺, and Na⁺ were decreased after cadmium treatment. Afterwards, using the drop test assay, the interactions between cadmium and the selected ions were investigated. The results suggested that the cytotoxicity of cadmium could be attributable to the interference of cadmium with the intracellular cation homoeostasis. Calcium channel transporter Cch1 participates in the intracellular uptake of cadmium. Additionally, Zn²⁺, Ca²⁺, Fe³⁺, Mg²⁺, and K⁺ can rescue the toxic effect of cadmium in yeast.     

The composition of natrophosphate (sodium fluoride phosphate hydrate)

Natrophosphate is a common trace mineral in alkaline rocks and a major salt in alkaline nuclear waste that complicates waste processing. Natrophosphate has historically been assigned the composition Na₇F(PO₄)₂·19H₂O, but this conflicts with a more recent solubility study that claimed natrophosphate is a solid solution of NaF and Na₃PO₄. It is not possible to model the solubility of natrophosphate in nuclear waste until this controversy is resolved. The present study mixed stock solutions of 0.9 M NaF and Na₃PO₄ at different ratios at 8 °C. The compositions of the liquid phase and wet natrophosphate sample were measured by ion chromatography. Plotting the tie-lines between the solid and liquid phase composition showed convergence on a single composition, indicating that natrophosphate is not a solid solution. The resulting composition is approximately the same as the composition first reported more than 140 years ago. Thus, this study resolves the long-standing controversy in the literature concerning the composition of natrophosphate.     

Biochemical speciation in chromium genotoxicity

The biochemical speciation of chromium compounds in mammalian cells is discussed with respect to uptake, metabolism, DNA binding and damaging. Whereas soluble hexavalent chromium is taken up rapidly and accumulated intracellularly after its reduction, compounds of trivalent chromium penetrate biomembranes about three orders of magnitude slower. Cr(VI) after its uptake is metabolised by electron donating compounds via Cr(V) to Cr(III) compounds. Chromium from various Cr(III) compounds, but not chromate, binds to chromatin in isolated cell nuclei. The DNA‐protein crosslinks and DNA strand breaks observed in rat liver and kidney after chromate administration are also found in vitro, when Cr(III) compounds (but not chromate) interacts with isolated nuclei. In the Chinese Hamster cell HGPRT mutation assay, three out of four tested Cr(III) complexes were found to be mutagenic. In a direct DNA strand break assay with supercoiled bacteriophage PM 2 DNA, neither chromate nor the four Cr(III) compounds tested caused nicks. However, the combined action of chromate plus glutathione as well as the isolated complex of pentavalent chromium, Na₄Cr(glutathione)₄, did cause DNA breaks. Reactive oxygen species are inferred to be the ultimate DNA nicking agents in this assay. In conclusion there appear to be two mechanisms of chromate genotoxicity; one with direct DNA damage caused by Cr(V) species and one via DNA‐protein crosslinks formed with Cr(III), the final reduction state of chromate.     

Biokinetic modeling of heavy metals in earthworms

Studies concerning bioaccumulation kinetics and bioconcentration factor (BCF) of heavy metals like zinc (Zn), lead (Pb), chromium (Cr), cadmium (Cd), and copper (Cu) in earthworm Eudrilus eugeniae tissues including integument, gizzard, clitellum, and head region were undertaken. Calculated BCF, predicted K _ow, and predicted K _oc showed a significant correlation between heavy metals in different earthworm tissues, in substrate spiked with heavy metals. The regression coefficient (r ²) between heavy metal uptake concentration and exposure time varied between 0.73 and 0.99, indicating significant correlation. The K _oc was a maximum of 13.9016 in case of Cu and integument at an exposure time of 100 days and a minimum of 0.1114 in case of Cr with respect to head at the same exposure time. Earthworms accumulated heavy metals following chronic exposure to municipal solid waste containing heavy metals. BCF and uptake rate kinetics of heavy metals were calculated and showed increased values in head tissue followed by integument.