Capacity of simultaneous removal of zinc and cadmium from contaminated media, by two microalgae isolated from a polluted site

Several aquatic environments have been contaminated with heavy metals dumped via industrial effluents. Numerous studies have been published regarding the removal of single metals from aqueous solutions by microalgal biomass. However, such studies do not reflect the actual problem associated with industrial effluents because usually more than one metal species is present. Here we studied the biosorption capacity of Zn²⁺ and Cd²⁺ as single- and binary-metal systems by two microalgae, Scenedesmus obliquus and Desmodesmus pleiomorphus, isolated from a polluted site in Northern Portugal. For each metal independently, D. pleiomorphus showed a higher metal sorption capacity than S. obliquus, at concentrations ranging from 60 to 300 mg/l (except 150 mg_Cd/l). Maximum amounts of Zn²⁺ and Cd²⁺ removed were 22.3 and 60.8 mg/g by S. obliquus, and 83.1 and 58.6 mg/g by D. pleiomorphus. In binary-metal solutions, S. obliquus was in general able to remove Zn²⁺ to higher extents than Cd²⁺, whereas the opposite was observed with D. pleiomorphus. The simultaneous uptake of Zn²⁺ and Cd²⁺ by both microalgae was considerably lower than that of their single-metal counterparts, at equivalent concentrations. Although microalgal uptake from binary-metal solutions was lower than from single-metal ones, the wild microalgae selected were able to efficiently take up mixtures of Zn²⁺ and Cd²⁺ up to 300 mg/l of both metals—thus materializing a promising bioremediation vector for polluted waters.     

Single and combined effects of heavy metals and hormones on lysosomes of haemolymph cells from the mussel Mytilus galloprovincialis

Effects of heavy metals on lysosomes were studied in living cells from the mussel (Mytilus galloprovincialis Lam.). Haemolymph cells were obtained from the mussel adductor muscle, stained with neutral red (NR), and analysed by digital imaging to evaluate NR retention times within lysosomes. Exposure to Hg²⁺, Cd²⁺ and Cu²⁺ induced a reduction of NR retention time, indicating lysosomal membrane destabilisation. The intensity of these effects was correlated with the metal affinity for sulfhydryls. In contrast, Zn²⁺ showed no effect on lysosomes. Moreover, 200 μM Zn²⁺ protected lysosomes against the effects of Cd²⁺ and Cu²⁺, but not against Hg²⁺. Cell loading with the fluorescent pH probe Lyso Sensor followed by digital imaging showed a rise of lysosomal pH induced by Cd²⁺ and Hg²⁺, while Zn²⁺ prevented the effect of Cd²⁺ and also partially that of Hg²⁺. The different protective effect of Zn²⁺ against Hg²⁺ suggests a dual action of Hg²⁺ on lysosomes, possibly involving both membrane destabilisation and proton pump inhibition. Cell exposure to 17 β-estradiol also caused a reduction of NR retention time, which was synergistic to that of Hg²⁺. This suggests a common pathway between metals and hormone, possibly involving Ca²⁺ signaling. Received: 17 November 1999 / Accepted: 29 June 2000     

Removal of heavy metals from aqueous solutions using activated carbon prepared from Cicer arietinum

Removal of Cu²⁺, Cd²⁺, Pb²⁺, and Zn²⁺ from aqueous solutions by activated carbon prepared from stems and seed hulls of Cicer arietinum, an agricultural solid waste, has been studied. The influence of various parameters, such as pH, contact time, adsorbent dose, and initial concentration of metal ions on removal was evaluated. The activated carbon was characterized by FT-IR spectroscopy, X-ray diffraction, and elemental analysis. Sorption isotherms were studied using Langmuir and Freundlich isotherm models. All experimental sorption data were fitted to the sorption models using nonlinear least-squares regression. The maximum adsorption capacity values for activated carbon prepared from Cicer arietinum waste for metal ions were 18 mg g^?1 (Cu²⁺), 18 mg g^?1 (Cd²⁺), 20 mg g^?1 (Pb²⁺), and 20 mg g^?1 (Zn²⁺), respectively. The Freundlich isotherm model fit was best, followed by the pseudo-second-order kinetic model. Desorption studies were carried out with dilute hydrochloric acid for quantitative recovery of the metal ions and for regeneration of the adsorbent.     

吐纳麝香与镉联合暴露对赤子爱胜蚓体内谷胱甘肽与金属硫蛋白的影响

广泛应用于个人护理产品和香味添加剂中的吐纳麝香(6-乙酰基-1,1,2,4,4,7-六甲基四氢萘,AHTN)是一种新型污染物,重金属镉(Cd2+)是土壤中常见的污染物,两者在土壤生态系统中存在联合暴露的可能。实验以赤子爱胜蚓为受试生物,通过24h暴露滤纸染毒实验测试了AHTN单一,Cd2+单一,以及AHTN与Cd2+联合暴露条件下蚯蚓体内谷胱甘肽(GSH)和金属硫蛋白(MT)的变化趋势。结果显示:Cd2+单一暴露时,GSH与MT随Cd剂量增加有明显上升趋势;AHTN单一暴露时,随着AHTN剂量增加,GSH与MT同步呈现先增多后减少的趋势;联合暴露情况下,AHTN在高剂量下对MT与GSH同样产生了抑制作用,使Cd2+对MT的诱导未达到Cd2+单一染毒时的水平。     

Inhibition of Na+/K+-ATPase and of active ion-transport functions in the gills of the shore crab Carcinus maenas induced by cadmium

Inhibition of Na⁺/K⁺-ATPase from gill plasma membranes of the shore crab Carcinus maenas by cadmium was investigated and compared with inhibitory effects by known antagonists (ouabain and Ca²⁺). For comparative considerations the Cd²⁺-inhibition of the enzyme from dog kidney was also tested. Na⁺/K⁺-ATPase from dog kidney and from crab gill differed greatly in sensitivity against ouabain. The inhibition constant K _i of the dog enzyme amounted to 9.1 × 10⁻⁷ mol l⁻¹, i.e. more than 300-fold smaller than the K _i of 2.9 × 10⁻⁴ mol l⁻¹ determined for the crab enzyme. Ca²⁺ inhibited the activity of Na⁺/K⁺-ATPase from crab gill plasma membranes with a K _i of 4.3 × 10⁻⁴ mol l⁻¹. The Na⁺/K⁺-ATPase from crab gill was inhibited by Cd²⁺ with a K _i of 9.1 × 10⁻⁵ mol l⁻¹. Cd²⁺ inhibited the Na⁺/K⁺-ATPase from dog kidney with a K _i (6.4 × 10⁻⁵ mol l⁻¹) comparable to that observed in the crab gill enzyme. Under experimental conditions Cd²⁺-inhibition of Na⁺/K⁺-ATPase was irreversible. Repeated washing, centrifugation and homogenization of the plasma membranes (four times) with Cd²⁺-free buffer did not restore any activity lost in the presence of 1 × 10⁻³ mol l⁻¹ Cd²⁺. Since ouabain-insensitive (nonspecific) ATPases in the plasma membrane fraction of crab gills were inhibited by Cd²⁺ in the same way as Na⁺/K⁺-ATPase, the heavy metal is considered as an unspecific ATPase inhibitor. Comparing these results with literature data on Cd²⁺-binding to electrophoretically separated proteins suggests that Na⁺/K⁺-ATPase is a Cd²⁺-binding enzyme. The results obtained on Na⁺/K⁺-ATPase were reflected by Cd²⁺-inhibition of the branchial ion-transport functions depending on this enzyme. The transepithelial short-circuit current of isolated gill half lamellae, a direct measure of area-specific active ion uptake, and the transepithelial potential difference of isolated, perfused whole gills, also indicative of active ion uptake, were inhibited by the heavy metal in a time- and dose-dependent mode. Remarkably these inhibitions were also irreversible. These findings are ecologically and biomedically significant: even when the actual environmental or tissue concentrations measured are low, biological microstructures such as Na⁺/K⁺-ATPase may accumulate the heavy metal by tight binding over prolonged periods until the first inhibitory effects occur. Received: 25 June 1997 / Accepted: 25 August 1997     

A simple ligandless microextraction method based on ionic liquid for the determination of trace cadmium in water and biological samples

A simple and efficient ionic liquid-based ligandless microextraction method has been developed for preconcentration of cadmium ions (Cd²⁺) as a step prior to its determination by flame atomic absorption spectrometry (FAAS) with a micro-sample introduction system. In this approach, the ionic liquid (IL) 1-butyl-3-methylimidazolium hexafluorophosphate [C₄mim][PF₆] and ethanol were used as extractant and dispersive solvents to preconcentrate the Cd²⁺ in different waters, acid digested scalp hair, and nail samples. Some analytical parameters influencing the extraction efficiency of Cd²⁺ and its subsequent determination, including pH, IL volume, dispersant solvent volume, sample volume, temperature, incubation time, and matrix effect, were optimized. Under optimal conditions, the limit of detection (LOD), limit of quantification (LOQ), and enhancement factor (EF) were 0.4 μg L^?1, 1.3 μg L^?1, and 50, respectively. The relative standard deviation (RSD) of 100 μgL^?1 Cd²⁺ was 4.3% (n = 6). The validity of the proposed method was checked by determining Cd²⁺ in certified reference material (TM-25.3 fortified water) and standard addition; the results showed sufficient recovery (>98%) of Cd²⁺ within the certified value. The method was applied for preconcentration and determination of cadmium in waters and biological samples.     

Application of Zr(IV) tungstate for removal of metal ions from aqueous solutions

A heteropolyacid Zr(IV) tungstate-based cation exchanger has been synthesized. An amorphous sample, prepared at pH 1.2 and having a Na⁺ ion exchange capacity of 0.92?meq?g^?1, was selected for further studies. Its physicochemical properties were determined using Fourier transform infrared spectrometer, X-ray diffraction, thermogravimetric, and scanning electron studies. To understand the cation exchange behavior of the material, distribution coefficients (K _d) for metal ions in various solvent systems were determined. Some important binary separations of metal ions, namely Mg²⁺–Bi³⁺, Cd²⁺–Bi³⁺, Fe³⁺–Bi³⁺, Th⁴⁺–Bi³⁺, and Fe³⁺–Zn²⁺, were achieved on such columns. The practical utility of these separations was demonstrated by separating Fe³⁺ and Zn²⁺ ions quantitatively in commercial pharmaceutical formulation. The cation exchanger has been successfully applied also for the treatment of industrial wastewater and a synthetic mixture. All the results suggests that Zr(IV) tungstate has excellent potential for the removal of metals from aqueous systems using packed columns of this material.     

In vitro toxic effects of heavy metals on fungal growth and phosphate-solubilising abilities of isolates obtained from Phragmites australis rhizosphere

In this research, we evaluated the toxic effect of metal ions on mycelial growth and phosphate-solubilising activity of soil-borne micromycetes isolated from the Phragmites australis rhizosphere using Pikovskaya-agar plates supplemented with four metal concentrations. The diameter growth rate (DGR) decreased as the metal concentration rise for all tested fungi. Trichoderma atroviride had the fastest growth rate (1.48?cm²?day^?1) and was the least susceptible to Al³⁺, Cd²⁺, Cr³⁺, Cu²⁺ and Pb²⁺ with a median effective concentration (MEC₅₀) of 12.19, 0.48, 4.51, 11.44 and 50.05?mM, respectively. Aspergillus japonicus was the most tolerant to Co²⁺, Ni²⁺ and Zn²⁺, with MEC₅₀ values of 3.36, 1.095 and 2.34?mM, respectively. Penicillium italicum was the most tolerant to Cr6⁺ (MEC₅₀?=?0.677?mM). The ability to solubilise phosphate remained, despite the decrease in the DGR, and P. italicum and Penicillium dipodomyicola had the highest Phosphate Solubilisation Indexes (PSIs) at 1.97 and 2.12, respectively. In particular, P. italicum recorded the highest PSI of all the studied isolates at 0.62?mM Cr³⁺ (PSI?=?4.74). A. japonicus and T. atroviride were the most tolerant isolates to all tested metals, which suggests that these isolates are promising candidates for further study with regard to mycoremediation and biofertilisation of metal-polluted soils.     

Shifts in Microbial Communities,Microbial Biomass and Organic Matter Mineralization for Three Mediterranean Soils Contaminated By Metals

Microbial communities (phospholipid fatty acid pattern, bacterial growing strategies, eco-physiological index (EPI) and total bacteria counts, as a number of heterotrophic cuhurable bacteria), substrate-induced respiration (SIR), and nitrogen mineralization were studied in three Mediterranean soils at three different depth levels (A, B and C). Soils were experimentally treated with a final concentration of 1000 ppm of trace metals (Cu²⁺, Zn²⁺, Al³⁺, Fe²⁺, Pb²⁺, Ni²⁺, Mn²⁺, Cr³⁺ and Cd²⁺). Soils were stored in 571 plastic containers for one year, and watered with 1001 during this period. Leachate was recovered through a bottom tap. Samples of the three depths were studied. Soil microbial communities showed different effects to other studies presented in the literature, but carried out on non-Mediterranean soils. Dramatic differences were found between treated soils and untreated ones, but not between soils or horizons. the treated soil displayed a decrease in CFUs, SIR N-mineralization and EPI together with a dominance of r-growing strategists. the relative moles percent of several PLFAs, especially 15:0, 16: 1ω7, cy17: 0, br18:0 and 18: 1ω7 decreased because of the pollution of soils, whereas 10Me16, 18:2ω6, cy19:0, i16:0 and br17:0 showed higher values than in untreated soils.     

Sorption of cadmium(II) and copper(II) by soil humic acids: temperature effects and sorption heterogeneity

Sorption by humic acids is known to modify the bioavailability and toxicity of metals in soils and aquatic systems. The sorption of cadmium(II) and copper(II) to two soil humic acids was measured at pH 6.0 using ion-selective electrode potentiometric titration at different temperatures. Sorption reactions were studied with all components in aqueous solution, or with the humates in suspension. Adsorption reactions were described using a multiple site-binding model, and a model assuming a continuous log-normal distribution of adsorption constants. Adsorption of Cu²⁺ was more favourable than adsorption of Cd²⁺. The log-normal distribution model provided the closest fit to observations and allowed parameterisation of adsorption data using a mean adsorption constant (log K _μ). Sorption of Cd²⁺ to dissolved humic acids increased slightly in extent and sorption affinity with increasing temperature, but the effect was small (log K _μ 2.96–3.15). A slightly greater temperature effect occurred for sorption of Cd²⁺ to solid-phase humic acids (log K _μ 1.30–2.08). Sorption of copper(II) to both aqueous- and colloidal-phase humates showed more pronounced temperature dependence, with extent of sorption, and sorption affinity, increasing with increasing temperature (log K _μ 3.4–4.9 in solution and 1.4–4.5 in suspension). The weaker adsorption of Cd²⁺ than Cu²⁺, and smaller temperature effects for dissolved humates than suspended humates, suggested that the observed temperature effects had a kinetic, rather than thermodynamic, origin. For any metal-to-ligand ratio, free metal ion concentration, and by inference metal bioavailability, decreased with increasing temperature. The consistency of the data with kinetic rather than thermodynamic control of metal bioavailability suggests that equilibrium modelling approaches to estimating bioavailability may be insufficient.     

Isolation and characterisation of cadmium-resistant bacteria from an industrially polluted coastal ecosystem on the southeast coast of India

A total of 35 bacterial strains were isolated from the industrially polluted Cuddalore coast, on the southeast coast of India. Of these, 17 strains were cadmium resistant and the remainder were sensitive. Six strains (C-1, C-8, C-10, C-12, C-14 and N-1) were selected based on high levels of cadmium tolerance (>150 mg L^?1) and were termed highly cadmium-resistant bacteria (HCRB). These HCRB were identified on the basis of morphological, biochemical and partial sequencing of their 16S rRNA genes. The antibiotic-susceptibility patterns and minimum inhibitory concentrations (MIC) of different metals (Cu²⁺, Pb²⁺ and Zn²⁺) against each HCRB were determined. Among the isolates, C-14 showed high degrees of metal and antibiotic resistance compared with other HCRB. Growth rates of HCRB at two different Cd²⁺ concentrations (50 and 100 mg L^?1) and under different metal conditions (Cd²⁺, Cu²⁺ and Pb²⁺) were also investigated. HCRB growth rates were lower in the metal-treated condition than in the untreated condition. Isolates C-14 and N-1 removed>80% of Cd²⁺ from cadmium-treated broth. However, isolate C-14 removed 92.3% of Cd²⁺ compared with 86.5% for isolate N-1. Bacteria showing residual growth rates under metal stress conditions might be useful in metal removal applications under growing conditions.     

Biomass and carbon budgeting of sustainable agroforestry systems as ecosystem service in Indian Himalayas

Adoption of agroforestry is paramount as a climate change mitigation and adaptation strategy. The assessment of plant biomass is crucial for understanding the vulnerability of biological systems to climate change. In the present study, agroforestry systems viz., agrisilviculture (AS), agrihorticulture (AH), agrihortisilviculture (AHS) and agrisilvihorticulture (ASH) were investigated for biomass production and carbon stock in vegetation as well as in soil in the Indian central Himalaya along the elevation i.e. E₁ (<1100 m), E₂ (1100–1400 m), E₃ (1400–1700 m), E₄ (1700–2000 m) and E₅ (>2000 m). Mean aboveground and belowground biomass were 73.9% and 26.1%, respectively, of total biomass (64.4 t ha^?1) in agroforestry systems. Fodder and/or timber trees accounted for 31% (in AHS) to 74% (in AS) of total biomass, while fruit trees accounted for 18% (in ASH) to 73% (in AH) of total biomass. The contribution of agriculture crops to total biomass fluctuated between 19% (in ASH) and 26% (in AH). Total vegetation biomass, soil carbon and total carbon density in agroforestry systems increased significantly along the elevation, with maximum biomass at elevation E₅ (32.0 t ha^?1, 64.7 t C ha^?1 and 96.7 t C ha^?1). Total biomass of vegetation among agroforestry systems differed significantly. Soil carbon stock was highest in AHS (59.5 t C ha^?1) and total carbon density (vegetation + soil) was highest in ASH (93.0 t C ha^?1). Thus, in Indian Himalayas, vegetation biomass, carbon stock, soil and total carbon (vegetation + soil) stock increased along the elevation.

Abbrviations: AG: aboveground; BG: belowground; WD: wood density; VOB: volume over bark; BEF: biomass expansion factor; AS: agrisilviculture; AH: agrihorticulture; ASH: agrisilvihorticulture; AHS: agrihortisilviculture; E: elevation; C: carbon; CO₂: carbon-di-oxide; IPCC: Intergovernmental Panel on Climate Change; DBH: diameter at breast height; AGBD: aboveground biomass density; BGBD: belowground biomass density; GSVD: growing stock volume density     

Large plasmids governing multiple resistances to heavy metals: A genetic approach∗

Gram negative bacteria classified as Alcaligenes eutrophus and carrying large resistance plasmids (generally two) were found in various industrial sites highly contaminated by heavy metals (Zn⁺⁺, Cu⁺⁺, Co⁺⁺,...). These strains were detected by DNA hybridization with a probe made with a 9kb fragment (ccz⁺ fragment) encoding for resistances to Cd⁺⁺, Co⁺⁺ and Zn⁺⁺, and cloned from plasmid pMOL30. This plasmid was isolated from the representative strain A. eutrophus CH34 which harbours the plasmids pMOL30 (240 kb) and pMOL28 (165 kb). Phenotypes related to pMOL28 and pMOL30 include the tolerance to Cd⁺⁺, Co⁺⁺, Cr0₄ ⁼, Cu⁺⁺, Hg⁺⁺, Ni⁺⁺, Pb⁺⁺ and Zn⁺⁺. The described genetic properties of these plasmids refer to some cloned or mapped functions and to some plasmid rearrangements. Plasmid pMOL85 (250 kb) which is related to pMOL30 was also described. Its host (A. eutrophus DS185) was isolated from a zinc desert. pMOL85 can efficiently self transfer in plasmidfree derivatives.     

Influence of americium-241 on the microbial population and biodegradation of organic waste

The present study investigated the influence of ²⁴¹Am on microbial growth and the degradation of organic waste. Leachate samples collected in a lysimeter were periodically analyzed for bacterial growth, under both aerobic and anaerobic conditions. ²⁴¹Am inhibited bacterial growth, and the degradation of organic matter was delayed in comparison with the control. Minimal inhibitory concentration assays and survival curves revealed that it inhibits the growth of Pseudomonas putida F1. The assay also revealed that ²⁴¹Am is more toxic than ²³⁸U, Zn²⁺ and Cd²⁺. This study further led to the finding of four new radionuclide-tolerant bacterial strains: Flavobacterium spp., Pseudomonas gladioli, Chryseobacterium indologenes and Ochrobactrum anthropi. The survival curves of P. gladioli, C. indologenes revealed that these bacteria are resistant to metal as consortia.     

Immobilized Lentinus edodes residue as absorbent for the enhancement of cadmium adsorption performance

To investigate the potential use of Lentinus edodes (L. edodes) residue for Cd²⁺ adsorption, poly alcohol Na alginate (PVA) was applied to immobilize it. The parameters including contact time, pH, adsorbent dosages, and coexisting metal ions were studied. The suitable pH for immobilized L. edodes was 4?C7 wider than that for raw L. edodes (pH 6?C7). In the presence of Pb²⁺ concentration varying from 0 to 30 mg·L^?1, the Cd²⁺ adsorption ratios declined by 6.71% and 47.45% for immobilized and raw L. edodes, respectively. While, with the coexisting ion Cu²⁺ concentration varied from 0 to 30 mg·L^?1, the Cd²⁺ adsorption ratios declined by 12.97% and 50.56% for immobilized and raw L. edodes, respectively. The Cd²⁺ adsorption isotherms in single-metal and dual-metal solutions were analyzed by using Langmuir, Freundlich, and Dubinin-Radushkevich models. The Cd²⁺ adsorption capacities (q _m) in single-metal solution were 6.448 mg·L^?1 and 2.832 mg·L^?1 for immobilized and raw L. edodes, respectively. The q _m of immobilized L. edodes were 1.850 mg Cd·g^?1 in Cd²⁺ + Pb²⁺ solution and 3.961 mg Cd·g^?1 in Cd²⁺ + Cu²⁺ solution, respectively. The Cd²⁺ adsorption processes subjected to both adsorbents follow pseudo-second-order model. Mechanism study showed the functional group of L. edodes was -OH, -NH, -CO, and PVA played an important role in metal adsorbing. Mining wastewater treatment test showed that PVA-SA-immobilized L. edodes was effective in mixed pollutant treatment even for wastewater containing metal ions in very low concentration.     

Toxic effects of dietary of Al3+ ions in tilapias (Oreochromis niloticus) and protective effect of Zn2+ ion

The lethal effects of aluminum ion (Al³⁺) in tilapia (Oreochromis niloticus) raised in concrete tanks were investigated. Tilapias were fed daily with commercial feed enriched with known concentrations of Al³⁺ and analyzed by differential pulse anodic stripping voltammetry (DPASV). The concentrations of Al³⁺ in feces, water, muscle tissue, viscera, and heads were determined every 3 months for a period of 365 days. The Tilapia head was the most affected tissue by Al³⁺. In general, Al³⁺ bioaccumulation reached the lethal dose (LD₅₀) after 335 days of experiment as follows: 34.9?mg?kg^?1 (muscle tissue), 88.2?mg?kg^?1 (viscera), and 126.9?mg?kg^?1 (head without gills). After determining Cu²⁺, Zn²⁺, and Ca²⁺ by absorption spectrometry, a decrease in the Ca²⁺ concentration was noted in the head during the experimental period. These observations were associated with the occurrence of a decalcification in the bone tissue in the presence of Al³⁺. In contrast, it was found that Zn²⁺ ions may act as a protective agent against Al³⁺-induced contamination.     

镉和铅对菲律宾蛤仔脂质过氧化及抗氧化酶活性的影响

为了研究亚致死浓度的重金属对海洋贝类的毒性效应,探讨其可能的作用机理,在实验生态条件下以菲律宾蛤仔(Ru-ditapes philip pinarum)为目标生物,采用半静态毒性实验方法,研究了不同浓度Cd2+(0.0948、0.237和0.474mg·L-1)和Pb2+(0.276、0.690和1.380mg·L-1)对菲律宾蛤仔鳃和消化腺组织中超氧化物歧化酶(SOD)、过氧化氢酶(CAT)活性以及丙二醛(MDA)含量的影响。结果显示:(1)鳃和消化腺中的抗氧化酶及MDA的变化呈现出类似的趋势,在胁迫初期,各浓度处理组菲律宾蛤仔鳃和消化腺组织SOD和CAT与对照组相比活性都显著升高(P<0.01),呈现出明显的诱导效应,而MDA含量与对照组相比差异不显著(P>0.05);随着胁迫时间的延长,高浓度Cd2+(0.474mg·L-1)和Pb2+(1.380mg·L-1)处理组中SOD、CAT活性快速下降,与对照组相比差异显著;低浓度处理组中的抗氧化活性虽然也较对照组有所下降,但总体下降幅度不如高浓度组明显,并且所历暴露时间较长。各浓度处理组中MDA含量变化一致,均呈现出先升高后降低的趋势,且含量均高于对照组。(2)通过相关性分析,菲律宾蛤仔消化腺组织中的SOD活性与Cd2+浓度的相关性大于鳃组织,与Pb2+浓度的相关性则小于鳃组织;消化腺组织中的CAT活性与Cd2+、Pb2+浓度呈抛物线型相关,与鳃组织CAT活性相关性不十分显著。这说明消化腺组织中SOD活性对Cd2+的敏感性大于鳃组织,消化腺组织中CAT活性对Cd2+、Pb2+的敏感性大于鳃组织。因此,菲律宾蛤仔消化腺中SOD、CAT对水环境中的重金属反应敏感,且存在一定的剂量-效应关系,消化腺组织中SOD和CAT活性与其他敏感性指标一起可以作为指示早期海洋重金属污染的生物标志物。     

Molecular dynamics of stability and structures in phytochelatin complexes with Zn,Cu, Fe,Mg, and Ca: Implications for metal detoxification

Phytochelatins, or (γ-glutamyl-cysteine) _n -glycine, are specialized peptides produced by plants and algae to mitigate toxic metal exposure, for instance in response to high levels of metals such as Cu, Cd, and Zn. Stability constants and structural characterization of metal–phytochelatin complexes are lacking. This information is required to gain mechanistic insights on the metal selectivity of phytochelatins. Here, we studied structural coordination and thermodynamic stability by performing molecular dynamics simulations of a fully hydrated phytochelatin molecule complexed with Ca²⁺, Mg²⁺, Fe²⁺, Zn²⁺, and Cu²⁺. Our results predict the following decreasing order for the thermodynamic stability of the phytochelatin complexes: Zn²⁺ ≥ Cu²⁺ ≥ Fe²⁺ > Mg²⁺ > Ca²⁺. The favorable binding energies with Zn²⁺ and Cu²⁺ over the other metal cations can be explained by shorter binding distances and greater coordination from carboxylate and keto O atoms. Conformational rearrangement of phytochelatin following metal chelation was captured by monitoring changes in the solvent-accessible volume. Accessibility of solvent molecules to the phytochelatin structure was inversely proportional to the distance between the coordinated ligands and the chelated metal. These new findings demonstrate the influence of the metal–phytochelatin structure on the metal-binding thermodynamics and the phytochelatin conformation, both of which are important to evaluate the intracellular role of phytochelatin in mediating algal response to toxic heavy metal exposure.     

重金属对禾谷镰刀菌的生长及毒素合成的影响

以禾谷镰刀菌为研究对象,研究了常见重金属(Cu、Pb、Zn、Cd)对禾谷镰刀菌菌株生长及其毒素合成的影响。研究结果表明,重金属对菌株的生长和其产毒能力均产生影响。Cu~(2+)和Cd~(2+)对菌株生长影响较大,随着浓度的增加对生长的抑制作用增强,当离子浓度分别为20 mg·L~(-1)和40 mg·L~(-1)时,能够完全抑制菌株生长。Zn~(2+)在0~160 mg·L~(-1)浓度范围内促进菌株生长,在10 mg·L~(-1)浓度下促进毒素合成。Pb~(2+)在察氏培养基中对菌株生长的影响没有明显规律可循,但是,随着Pb~(2+)浓度增加,抑制毒素合成作用增强。