The redox state and activity of superoxide dismutase classes in Arabidopsis thaliana under cadmium or copper stress

The redox state of glutathione and ascorbate as well as the activity of superoxide dismutase classes were determined in leaves of Arabidopsis thaliana grown for seven days in the nutrient solution containing 0, 5 and 50 microM Cd or Cu excess. A decrease in GSH/GSSG ratio was found in plants under Cd and Cu stress. In the plants exposed to Cu stress the activity of all SOD classes increased. However, in the plants treated with Cd the activity of FeSOD and MnSOD was elevated, but CuZnSOD activity was diminished in comparison with control. In these plants the activity of SOD classes was dependent on both the GSH/GSSG and AA/DHA ratios, while in those exposed to Cu excess - on the GSH/GSSG ratio. Differences were shown in the changes both in redox state and activity of SOD classes caused by the metals differing in physiochemical properties. Moreover, relationships between changes in SOD class activities and ROS levels were discussed.     

Changes in photochemical and antioxidant enzyme activities in maize (Zea mays L.) leaves exposed to excess copper

Changes in photosynthetic and antioxidant activities in maize (Zea mays L.) leaves of cultivars 3223 and 31G98 exposed to excess copper (Cu) were investigated. Cu treatment reduced the shoot and root length of both cultivars. No significant difference of Cu accumulation in the roots of both cultivars was observed while the cultivar 3223 accumulated significantly higher Cu in leaves than 31G98. The observed decreases in effective quantum efficiency of PSII, ETR and qP indicate an over excitation of photochemical system in 3223 compared to 31G98. The leaf chlorophyll and carotenoid contents of both cultivars decreased with increasing Cu concentration. A far higher production of anthocyanins in 31G98 has been observed than that of 3223. At 1.5 mM Cu concentration, all antioxidant enzyme activities increased in leaves of the cultivar 31G98 while there were no significant changes in SOD and GR activities in 3223 compared to the control except increased APX and POD activities. The lower Cu accumulation in leaves and higher antioxidant enzyme activities in 31G98 suggested an enhanced tolerance capacity of this cultivar to protect the plant from oxidative damage.     

Role of salicylic acid in alleviating oxidative damage in rice roots (Oryza sativa) subjected to cadmium stress

Time-dependent changes in enzymatic and non-enzymatic antioxidants, and lipid peroxidation were investigated in roots of rice (Oryza sativa) grown hydroponically with Cd, with or without pretreatment of salicylic acid (SA). Exposure to 50 microM Cd significantly decreased root growth, and activities of superoxide dismutase (SOD), catalase (CAT) and peroxidase (POD), but increased the concentrations of H(2)O(2), malondialdehyde (MDA), ascorbic acid (AsA), glutathione (GSH) and non-protein thiols (NPT). However, pretreatment with 10 microM SA enhanced the activities of antioxidant enzymes and the concentrations of non-enzymatic antioxidants, but lowered the concentrations of H(2)O(2) and MDA in the Cd-stressed rice compared with the Cd treatment alone. Pretreatment with SA alleviated the Cd-induced inhibition of root growth. The results showed that pretreatment with SA enhanced the antioxidant defense activities in Cd-stressed rice, thus alleviating Cd-induced oxidative damage and enhancing Cd tolerance. The possible mechanism of SA-induced H(2)O(2) signaling in mediating Cd tolerance was discussed.     

Enhancement of copper and cadmium adsorption on kaolin by the presence of humic acids

The competitive adsorption equilibrium isotherms of Cu²⁺ and Cd²⁺ on kaolin have been measured at 298 K, in the presence and the absence of humic acids (HAs). HAs were found to enhance the metal adsorption capacity of mineral surfaces, in particular kaolin. This enhancement was also observed in the competitive adsorption of copper and cadmium on kaolin and kaolin–HA complex. This competitive adsorption shows that the presence of Cd²⁺ has not an important effect on Cu²⁺ adsorption, whereas a dramatic decrease is observed on the adsorption of Cd²⁺ in the presence of Cu²⁺. The Freundlich isotherm equation was found to provide an excellent fit to the experimental data. These results were compared with the independent adsorption of both heavy metals.     

Overexpressing GSH1 and AsPCS1 simultaneously increases the tolerance and accumulation of cadmium and arsenic in Arabidopsis thaliana

The goal of this study was to develop transgenic plants with increased tolerance for and accumulation of heavy metals and metalloids from soil by simultaneous overexpression of AsPCS1 and GSH1 (derived from garlic and baker's yeast) in Arabidopsis thaliana. Phytochelatins (PCs) and glutathione (GSH) are the main binding peptides involved in chelating heavy metal ions in plants and other living organisms. Single-gene transgenic lines had higher tolerance to and accumulated more Cd and As than wild-type. Compared to single-gene transgenic lines, dual-gene transformants exhibited significantly higher tolerance to and accumulated more Cd and As. One of the dual-gene transgenic lines, PG1, accumulated twice the amount of Cd as single-gene transgenic lines. Simultaneous overexpression of AsPCS1 and GSH1 led to elevated total PC production in transgenic Arabidopsis. These results indicate that such a stacking of modified genes is capable of increasing Cd and As tolerance and accumulation in transgenic lines, and represents a highly promising new tool for use in phytoremediation efforts.     

Biological and photochemical degradation rates of diethylenetriaminepentaacetic acid (DTPA) in the presence and absence of Fe(III)

The environmental fate of ethylenediaminetetraacetic acid (EDTA) has been extensively studied, while much less is known about the environmental behaviour of diethylenetriaminepentaacetic acid (DTPA). In this study, it was confirmed that DTPA is persistent toward biodegradation. The biodegradability of DTPA was investigated in the absence and in the presence of Fe(III) by using CO2 evolution test and Manometric respirometry test. The CO2 evolution and oxygen uptake of iron-free (DTPA was added as free acid) and Fe(III)DTPA were less than in inoculum blank. Possible inhibitor effect was analysed by testing biodegradation of sodium benzoate with and without iron-free or Fe(III)DTPA in the Manometric respirometry test. Only slight inhibition was observed when DTPA was added as free acid. Photodegradation of iron-free DTPA and Fe(III)-DTPA complex was studied by using sunlight and UV radiation at the range 315-400 nm emitted by black light lamps. The results indicate that DTPA added as free acid degrades photochemically in humic lake water. Fe(III)DTPA was shown to be very photolabile in humic lake water in the summer; the photochemical half-life was below one hour. Photodegradation products were identified by the mass spectrometric technique (GC-MS). It was shown that photodegradation of Fe(III)DTPA does not result in total mineralization of the compound. Diethylenetriaminetetraacetic acid, diethylenetriaminetriacetic acid, ethylenediaminetriacetic acid, N,N'- and/or N,N-ethylenediaminediacetic acid, iminodiacetate, ethylenediaminemonoacetic acid and glycine were identified as photodegradation products of Fe(III)DTPA. Based on these observations, we propose a photodegradation pathway for Fe(III)DTPA.     

Variation of zinc and copper in metallothionein-like protein in killifish (Oryzias latipes) exposed to cadmium

Killifish (Oryzias latipes) were exposed for 0, 24, 48 and 168 hours to cadmium solution. The hepatic cytoplasm was fractionated by using Sephadex G-75 and the content of zinc, copper and cadmium in the fractions was measured. Cadmium content in the metallothionein fraction increased with increase of exposure time. Zinc content in the metallothionein fraction was reduced at early exposure time and increased after prolonged exposure. Copper content in the metallothionein fraction was unchanged. It is shown that zinc bound to thionein in the liver is partially replaced by cadmium and that at least two isomers of metallothionein occur in this fish.     

Phytotoxicity of short-term exposure to excess zinc or copper in Scots pine seedlings in relation to growth,water status,nutrient balance,and antioxidative activity

The toxic effects of heavy metals pose a significant threat to the productivity and stability of forest ecosystems. Changes in the agrochemical properties of polluted forest soils due to global climate changes can increase the bioavailability of previously immobilized heavy metals. To test this hypothesis, we studied the effects of short-term shock exposure to ZnSO₄ (50, 150, 300 μM) or CuSO₄ (2.5, 5, 10 μM) in hydroculture on 4- to 6-week-old seedlings of Scots pine (Pinus sylvestris L.) with well-developed root systems. The effects of the excess heavy metals on mineral nutrients and the functioning of low-molecular-weight antioxidants and glutathione in protecting plants from oxidative damage were studied. Even short-term exposure to exogenous metals led to their rapid accumulation in the root system and their subsequent transport to aboveground organs. An increase in the 4-hydroxyalkenals content in seedling needles exposed to excess Cu led to an increase in the content of proanthocyanidins and catechins, which act as scavengers of reactive oxygen species. The impact of both metals led to the rapid development of mineral nutrient imbalances in the seedlings, which were most pronounced in the presence of excess Zn. Exposure to excess Zn led to a disruption in the translocation of Fe and a decrease in the Fe content in the needles. The most dramatic consequence of Zn exposure was the development of Mn deficiency in the roots, which was the likely cause of the inhibition of phenolic compound synthesis. A deficiency in phenolic compounds can have serious environmental consequences for pine populations that are at risk of contamination by Zn and Cu salts.

     

Foliar application of aspartic acid lowers cadmium uptake and Cd-induced oxidative stress in rice under Cd stress

Environmental Science and Pollution Research - Cadmium (Cd) contamination of farmland soils is a widespread problem around the globe, and rice (Oryza sativa L.) tends to accumulate more Cd and is...     

Effects of cadmium on the photosynthetic activity in mature and young leaves of soybean plants

Cadmium (Cd) is a widely spread pollutant and can be easily taken up by crop from soil, resulting in a serious health issue for humans. The objective of this study was to comparatively investigate the photosynthetic activity, chlorophyll a fluorescence, chlorophyll contents, and spectral reflectance in mature and young leaves of soybean plants after being treated with different concentrations of Cd for 10 days. The photosynthetic rate, chlorophyll contents, actual photochemical efficiency of PSII, and photochemical quenching in the young leaves decreased more significantly with increasing concentrations of Cd in the nutrient solution, compared with those in the mature leaves, though the young leaves had less Cd concentrations. Thus, there was more excessive excited energy produced in the young leaves than that in the mature leaves. In the young leaves, due to more excessive excited energy, more reactive oxygen species may be generated, which further damaged the photosynthetic apparatus. It was supported by the fact that the decrease of reflectance in near-infrared wavelengths of the young leaves was more noticeable than that of the mature leaves. In addition, the chlorophyll a fluorescence transients of the young leaves was significantly different from that in the mature leaves, indicating that the electron transport of young leaves were inhibited much more severely than that of the mature leaves. These observations imply that the responses of photosynthetic activity of soybean leaves to Cd stress depend on their growth stage, and the Cd-induced inhibition of photosynthetic activity might be attributed to the decrease in chlorophyll contents and the decrease in mesophyll CO₂ assimilation ability cause by the Cd, which further decreased the consumption of ATP and NADPH, leading to accumulation of NADPH on the acceptor sides of the PSI, and then feedback inhibited electron transport in chloroplasts.     

Arsenite oxidation and arsenic adsorption on birnessite in the absence and the presence of citrate or EDTA

Birnessite not only oxidizes arsenite into arsenate but also interacts with organic matter in various ways. However, effects of organic matter on interaction between As and birnessite remain unclear. This study investigated effects of citrate and EDTA (3.12 and 2.05 mM, respectively) on oxidation of As(III) (1.07 mM) and adsorption of As(V) (0.67 mM) on birnessite (5.19 mM as Mn) at near-neutral pH. We found that As(V) adsorption on birnessite was enhanced by citrate and EDTA, which resulted from the increase in active adsorption sites via dissolution of birnessite. In comparison with citrate batches, more As was adsorbed on birnessite in EDTA batches, where dissolved Mn was mainly presented as Mn(III)-EDTA complex. Citrate or EDTA-induced dissolution of birnessite did not decrease the As(III) oxidation rate in the initial stage where As(III) oxidation rate was rapid. Afterwards, As(III) oxidation was conspicuously suppressed in citrate-amended batches, which was mainly attributed to the decrease in adsorption sites by adsorption of citrate/Mn(II)-citrate complex. This suppression was enhanced by the increase in concentrations of dissolved Mn(II). Citrate inhibited As adsorption after As(III) oxidation due to the strong competitive adsorption of citrate/Mn(II)-citrate complex. However, the As(III) oxidation rate was increased in EDTA-amended batches in the late stage, which mainly derived from the increase in the active sites via birnessite dissolution. The strong complexation ability of EDTA led to formation of Mn(III)-EDTA complex. Arsenic adsorption was not affected due to the limited competitive adsorption of the complex on the solid. This work reveals the critical role of low molecular weight organic acids in geochemical behaviors of As and Mn in aqueous environment.

     

Investigation of the generation of hydroxyl radicals and their oxidative role in the presence of heterogeneous copper catalysts

The presence and impact of hydroxyl radicals generated via the catalytic decomposition of H(2)O(2) over heterogeneous copper catalysts were investigated by using two detection methods, an electron spin resonance-spin trapping method and a chemical probe method. Detection of the (5,5-dimethyl-1-pyrroline-N-oxide)-OH adduct signal and formation of 4-chlorocatechol during the oxidation of a 4-chlorophenol substrate demonstrated that the three heterogeneous copper catalysts employed here (CuO, Cu/Al(2)O(3) and CuO.ZnO/Al(2)O(3)) were capable of generating hydroxyl radicals in combination with H(2)O(2). The oxidative mechanism of the hydroxyl radical in the presence of heterogeneous copper catalysts is discussed with regard to the further oxidation of the (5,5-dimethyl-1-pyrroline-N-oxide)-OH adduct and hydroxylated products of 4-chlorophenol oxidation. Interestingly, integration of the 5,5-dimethyl-1-pyrroline-N-oxide-OH adduct signal could not be used to reliably measure the total amount of hydroxyl radicals generated as a result of oxidative attack on the adduct. This may be as a result of locally higher hydroxyl radical concentrations in the presence of a heterogeneous catalyst leading to further unwanted oxidation of the (5,5-dimethyl-1-pyrroline-N-oxide)-OH.     

Mitigation of peroxidative stress for barley exposed to cadmium in the presence of water-extractable organic matter from compost-like materials

The effects of water-extractable organic matter (WEOM) from compost-like materials on peroxidative stress were investigated for hydroponic culture of barley exposed to Cd. In the presence of WEOM, lipoxygenase activity and malondialdehyde, indices of peroxidative stress in barley, were significantly reduced, compared to those with Cd alone (5 μM) for a 30-d culture (p < 0.05). In addition, Cd uptake in the presence of WEOM samples was significantly lower than that in their absence (p < 0.05). These results indicate that the addition of WEOM can be effective in mitigating the peroxidative stress in barley exposed to Cd. Of the total Cd in the solution, 7–8% was complexed with WEOM, indicating that the complexation of Cd with WEOM is a minor factor in reducing Cd-induced stress in barley. The WEOM sample was purified by cation-exchange column and ultrafiltration to remove the nutrient minerals, such as Ca, Mg and Fe. When the purified WEOM was employed for hydroponic culture in the presence of Cd, significant decreases in peroxidative stress and Cd uptake were observed (p < 0.05). These results show that the organic components in WEOM contribute to the mitigation of peroxidative stress in barley exposed to Cd.     

TiO2 nanoparticles potentiated the cytotoxicity,oxidative stress and apoptosis response of cadmium in two different human cells

Environmental Science and Pollution Research - Widespread application of titanium dioxide nanoparticles (nTiO2) and ubiquitous cadmium (Cd) pollution may increase their chance of co-existence in...     

Seasonal variations in the concentrations of cadmium, copper, lead and zinc in leaves of the horse chesnut (Aesculus hippocastanum L.)

The concentrations of cadmium, copper, lead and zinc have been measured in the leaves of a deciduous tree the horse chestnut (Aesculus hippocastanum L.) over the period of their lifetime (7 months). The average concentrations for the total sample based on ash weight are: (microg g(-1)) cadmium, 0.197; copper, 129; lead, 294; and zinc, 299. The temporal trends in the concentrations of the metals can be related to their dominant source. Copper and zinc concentrations are highest in the new leaves and decrease with time, suggesting the main source of the elements are uptake from the soil. The decrease occurs partly because of dilution by leaf material as it increases over the growing period. In the case of zinc, however, aerial deposits appear to be also a significant source. Lead concentrations, on the other hand, show an increase with time, which can be related to increasing deposits from aerosol lead arising from the combustion of petrol lead. The increase is enough to offset the dilution effect. For cadmium there is no significant trend, but the tendency is a decrease with time. It is not possible, however, to distinguish between soil uptake and aerial deposit as both are small compared with increase in leaf material.     

Photolysis of the herbicide bispyribac sodium in aqueous medium under the influence of UV and sunlight in presence or absence of sensitizers

The photolysis of a rice herbicide Bispyribac sodium (Sodium 2, 6-bis [(4, 6-dimethoxypyrimidin-2-yl) oxy] benzoate) has been studied in different aqueous medium (distilled water, pond water and Irrigation water) under the influence of UV (λ max ≥ 250 nm) and sunlight in presence or absence of sensitizers (TiO₂ and KNO₃). The study was conducted under laboratory simulated condition which made it possible to evaluate the contribution of different factors viz. source of irradiation, solvent and sensitizers towards the photolysis of bispyribac sodium. The photodegradation proceeds via first order reaction Kinetics in all the cases. Five photo metabolites (M₁-M₅) were isolated in pure form by column chromatographic method from the irradiation system under UV influenced and TiO₂ as sensitizer. From the different spectral data (IR, NMR, UV-VIS, Mass) the structure of these five metabolites were assigned as M₁ (Phenol), M₂ [2, 6-Dihydroxy benzoic acid], M₃ [2, 6-bis [(4, 6 dimethoxypyrimidin-2yl) oxy] benzoic acid], M₄ [2-(3-Hydroxy-phenoxy)-pyrimidine-4, 6-diol] and M₅ as [2,4-Dihydroxy-3, 5-dimethoxy-6-(4-methoxy pyrimidine-2-yloxy)-benzoic acid]. Moreover, another six photometabolites (M₆-M₁₁) were identified from the different irradiation system on the basis of Micromass analysis. On the basis of MS/MS data analysis, the structure of these six photometabolites were assigned as M₆ [2-(4, 6-Dimethoxy-pyrimidin-2-yloxy)-6-hydroxy-benzoic acid], M₇ [2-Hydroxy-6-(4-hydroxy-6-methoxy-pyrimidin-2-yloxy)-benzoic acid], M₈ [4, 6-Dimethoxy-pyrimidin-2-ol], M₉ [6-Methoxy-pyrimidine-2, 4-diol], M₁₀ [2-Hydroxy-6-(pyrimidin-2-yloxy)-benzoic acid] and M₁₁ [2, 4, 6-Trimethoxy-pyrimidine]. The plausible Photodegradation pathways of bispyribac sodium in the present investigation were portrayed which proceeds via hydrolysis, hydrolytic cleavage, O-dealkylation, decarboxylation, dehydroxylation, O-alkylation and hydroxylation.     

The tolerance of grapevine rootstocks to copper excess and to the use of calcium and phosphorus to mitigate its phytotoxicity

Environmental Science and Pollution Research - High soil copper (Cu) concentrations in vineyards can cause phytotoxicity to grapevine rootstocks. In order to mitigate toxicity, the use of grapevine...     

Variation in sensitivity to cadmium among genetically characterized laboratory strains of the midge Chironomus riparius

Estimating the extent of intraspecific variation in sensitivity to contaminant exposure is important in order to explain variation in the outcome of toxicity tests and to predict the effects of chemical stress on natural populations of plants and animals. However, only few studies provide evident data concerning intraspecific variation in life-history traits caused by a differential response to chemical stress. In this study, we compared the life-history response of six laboratory strains of the midge Chironomus riparius to cadmium exposure in a full life-cycle assay. In addition, the level of genetic variation in all strains was measured at five variable microsatellite loci. Several significant differences in life-history traits among the strains were observed in controls and cadmium treatments. The extent of variation among strains was largest at moderate cadmium concentration (0.42 mg Cd/kg dw). At increased Cd concentrations all strains showed similar levels of high mortality and reduced reproductive success. All strains exhibited considerable levels of genetic impoverishment compared to field populations. Strains with low genetic variation showed reduced fitness in the controls and were more susceptible to Cd exposure. For instance, no reproductive success in the lowest Cd treatment was observed for the strain with the lowest level of genetic diversity. In contrast, this Cd concentration had no negative effects on life-history traits of more variable strains. These results confirm recent findings, that inbreeding and reduced genetic variation influence the reaction of populations towards environmental stress. In addition, we show that the level of genetic variation and inbreeding directly influences the outcome of toxicity tests and contributes to the lack of reproducibility of test results among laboratories.     

Multi-generation toxicity of zinc, cadmium, copper and lead to the potworm Enchytraeus albidus

In standard chronic terrestrial toxicity tests with invertebrates, adult organisms are exposed to the contaminants and the number of offspring is quantified. These procedures do not allow the assessment of possible effects on all life stages of the organism, which may lead to an underestimation of the toxicity of the test substance. To evaluate the importance of this issue, the potworm Enchytraeus albidus was exposed to zinc, cadmium, copper and lead for two subsequent generations. Juvenile production was assessed for both generations. Considering the variability of metal toxicity data reported in the literature, it is concluded that the two generation assay did not markedly increase the sensitivity of the standard E. albidus test for the tested metals. Therefore, toxicity data obtained with the proposed test guideline with E. albidus are protective for all life stages.