Differences in uptake and translocation of selenate and selenite by the weeping willow and hybrid willow

BACKGROUND, AIM, AND SCOPE: Due to its essentiality, deficiency, and toxicity to living organisms and the extensive use in industrial activities, selenium (Se) has become an element of global environmental and health concern. Se removal from contaminated sites using physical, chemical, and engineering techniques is quite complicated and expensive. The goal of this study was to investigate uptake and translocation of Se in willows and to provide quantitative information for field application whether Se phytoremediation is feasible and ecologically safe. MATERIALS AND METHODS: Intact pre-rooted plants of hybrid willows (Salix matsudana Koidz x alba L.) and weeping willows (Salix babylonica L.) were grown hydroponically and treated with selenite or selenate at 24.0 +/- 1 degrees C for 144 h. Removal of leaves was also performed as a treatment to quantify the effect of transpiration on translocation and volatilization of Se. At the end of the study, total Se in the hydroponic solution and in different parts of plant tissues was analyzed quantitatively by hydride generation-atomic fluorescence spectrometry. The capacity of willows to assimilate both chemical forms of Se was also evaluated using detached leaves and roots in sealed glass vessels in vivo. Translocation efficiency of Se in both plants was estimated. RESULTS: Significant amounts of the applied selenite and selenate were eliminated from plant growth media by willows during the period of incubation. Both willows showed a significantly higher removal rate for selenate than for selenite (p < 0.05). Substantial differences existed in the distribution of both chemical forms of Se in plant materials: lower stems and roots were the major sites for accumulation of selenite and selenate, respectively. Translocation efficiency for selenite was significantly higher than that for selenate in both willow species (p < 0.01). Compared to the intact trees, remarkable decrease in the removal rate of both chemical forms of Se was found for willows without any leaves (p < 0.01). Volatilization of Se by plant leaves was estimated to be approximately 10% of the total applied selenite or selenate. Significant reduction (>20%) of selenate was observed in the sealed vessel with excised roots of willows, whereas trace amounts of selenite were eliminated from the hydroponic solution in the presence of roots. Detached leaves from neither of them reduced the concentration of selenite or selenate in the solution. DISCUSSION: Due to the significant difference in the removal rate and the distribution of the two chemical forms of Se in plant materials, the conversion of selenate to selenite in hydroponic solution prior to uptake and within plant tissues is unlikely. An independent uptake and translocation mechanisms are likely to exist for each Se chemical species. Uptake of selenate is mediated possibly through an active transport mechanism, whereas that of selenite may possibly depend on plant transpiration. Uptake velocities of selenite are linear (zero-order kinetics), while selenate removal processes obey first-order kinetics. In experiments with detached leaves in closed bottles, the cuticle of leaves was the major obstacle to extract both chemical forms of Se from the hydroponic solution. Phytovolatilization is a biological process playing an important role in Se removal. CONCLUSIONS: Although faster removal rates of selenate than selenite from plant growth media were observed by both willow species, selenite in plant materials was more mobile than selenate. Significant decrease in removal rates of both chemical forms of Se was detected for willows without any leaves. Significant differences in extraction, assimilation and transport pathways for selenite and selenate exist in willow trees. RECOMMENDATIONS AND PERSPECTIVES: Phytoremediation of Se is an attractive approach of cleaning up Se contaminated environmental sites. More detailed investigation on the assimilation of Se in plant roots and transport in tissues will provide further biochemical evidence to explain the differences in uptake and translocation mechanisms between selenite and selenate in willows. A relevant phytoremediation scheme can then be designed to clean up Se contaminated sites. Willows show a great potential for uptake, assimilation and translocation of both selenite and selenate. Phytotreatment of Se is potentially an efficient and practical technology for cleaning up contaminated environmental sites.     

Accumulation and excretion of organophosphorous pesticides by willow shiner

Bioconcentration and excretion of 8 organophosphorous pesticides were studied for willow shiner ( ). The average bioconcentration factors (BCF) in the whole body of the fish after 24 – 168 hr exposure were 0.8 for dichlorvos, 76 for salithion, 18 for methidathion, 29 for pyridaphenthion, 481 for fenthion and 36 for phosmet, Further, the BCF values of the other pesticides after 168 hr exposure were 713 for phenthoate and 1682 for EPN. The correlation between n-octanol-water partition coefficients (P_OW) and BCF in willow shiner was investigated for 19 pesticides studied here and already reported. The correlation factor (r) was not so high (0.6819, n=19) but higher (0.9085, n=18) in case excluding captan. The excretion rate constants (k) from the whole body of willow shiner were 0.20 hr⁻¹ for salthion, 0.05 hr⁻¹ for phenthoate, 0.27 hr⁻¹ for methidathion, 0.20 hr⁻¹ for pyridaphenthion, 0.07 hr⁻¹ for fenthion, 0.04 hr⁻¹ for EPN and 0.28 hr⁻¹ for phosmet.     

活性炭吸附苯酚及其超声波再生效果

研究了颗粒活性炭(GAC)对苯酚的吸附能力,确定GAC的吸附平衡时间,探讨超声波再生吸附苯酚活性炭的影响因素。实验结果表明:6 h后GAC吸附100 mL浓度为250 mg/L的苯酚水样达到平衡,最大平衡吸附量为16.24 mg/g,去除率为70.5%。再生条件为再生液温度30℃,超声再生时间20 min,解析液为0.25 mol/L氢氧化钠溶液,此时GAC再生效果为86.1%。     

Removal of organic polyelectrolytes and their metal complexes by adsorption onto xonotlite

Natural organic polyelectrolytes (humic and fulvic acids) and their metal complexes were removed by adsorption onto xonotlite. The removal percentages of humic and fulvic acids by xonotlite were approximately 80% and 30%, respectively. Humic acid removal from solution by adsorption onto xonotlite took place more readily than fulvic acid removal. The molecular weight distributions of the humic substances remaining in solution after adsorption with the xonotlite were measured with size exclusion chromatography. A comparison of molecular weight distributions demonstrated conclusively that large molecular weight components were adsorbed preferentially, indicating that adsorption efficiency depends on the number of functional groups of humic substances. Furthermore, the surface topography of the adsorbent was observed before and after adsorption by scanning electron microscopy. The calculated heat of adsorption was of 330 kJ mol(-1) which was evaluated from the Clapeyron-Clausius equation. Therefore, the adsorption type can be considered chemical. Since xonotlite can be easily synthesized and obtained at low cost, the adsorption method of humic and fulvic acids is superior to their precipitation.     

The role of root hairs in cadmium acquisition by barley

The role of root hairs in Cd acquisition from soil was investigated in three pot experiments using a root hairless mutant (bald root barley, brb) and its wild-type (WT) cultivar of barley (Hordeum vulgare). brb had significantly lower concentrations and lower total amounts of Cd in shoots than WT. The Cd uptake efficiency based on total root length was 8-45% lower in brb than in WT. The difference between brb and WT increased with increasing extractable Cd in soil under the experimental conditions used. Additions of phosphate to soil decreased Cd extractability. Both soil and foliar additions of phosphate decreased root length, and root hair formation in WT. These effects resulted in decreased Cd uptake with increasing P supply. Cd uptake in WT correlated significantly with root length, root hair length and density, and soil extractable Cd. Root hairs contribute significantly to Cd uptake by barley.     

Mutual effects of cadmium and phosphate on their adsorption and desorption by goethite

Adsorption of cadmium (Cd) and phosphate by oxides or soils has been extensively studied, but the adsorption/desorption kinetics and mutual effects of these two species in co-existing systems has received little attention. In this study, a batch equilibration method was used to investigate the effect of phosphate and its application time on Cd adsorption and desorption on goethite. The influence of Cd and its application time on phosphate sorption and desorption kinetics was also determined. For Cd adsorption, phosphate was introduced into the system by two sequences: pre-treating goethite at 40 (degrees)C for 1 week, and applying with Cd simultaneously. Similarly, for phosphate sorption, Cd was applied by pre-treating goethite at 40 (degrees)C for 1 week or simultaneous addition with phosphate. Results demonstrated that phosphate added to goethite enhanced Cd adsorption, and facilitated Cd release as compared to untreated goethite. Cadmium had slightly higher adsorption, but a significantly faster desorption rate from the goethite simultaneously treated with phosphate and Cd, as compared to phosphate-pretreated goethite. Cadmium and its application time had little impact on phosphate sorption by goethite. However, phosphate desorption kinetics was affected by Cd application time. When the sorption time was short (15 min), phosphate desorption was faster from the goethite that was simultaneously treated with phosphate and Cd, as compared to Cd pretreated or untreated goethite. In contrast, a longer sorption time (4 weeks) resulted in a higher desorption rate of phosphate from Cd pretreated goethite than simultaneously phosphate-Cd treated goethite. This study provided useful information on adsorption/desorption kinetics in complicated Cd-phosphate-goethite systems.     

Cadmium uptake by the water hyacinth: Effects of root mass,solution volume,complexers and other metal ions1

At a fixed Cd²⁺ concentration water hyacinth ($\text{Eichhornia crassipes}$) plants with greater root mass (dry weight) take up more metal ions as a function of time, and more metal ions are taken up by a plant as the solution volume is increased. Experiments in which several different metal ion complexers were present suggest that (1) the roots possess sites which initially reversibly bind free Cd²⁺, (2) some added complexers can compete with these root sites for free Cd²⁺, and (3) with time Cd²⁺ bound to the roots is translocated into into the root tissues effectively removing it from the equilibrium processes in solution. Many metal ions are taken up by the plant but only the micronutrient Zn²⁺ competes well with Cd²⁺ for uptake. Thus, there may be binding sites on the roots for specific metal ions.     

Cadmium adsorption and desorption behaviour on goethite at low equilibrium concentrations: effects of pH and index cations

The transport and bioavailability of cadmium is governed mainly by its adsorption-desorption reactions with minerals such as goethite--a common iron oxide mineral in variable charged and highly weathered tropical soils. Soil factors such as pH, temperature, solution Cd concentration, ionic strength and ageing affect Cd adsorption on goethite. The desorption behaviour of Cd from goethite at low concentrations is not fully understood. This study investigates the adsorption-desorption of Cd at low Cd concentrations (Cd adsorbed on goethite from 20 to 300 microM Cd solutions) in Na and Ca nitrate solutions of 0.03 M nominal ionic strengths. Synthetic goethite prepared by ageing a ferric hydroxide gel at high pH and room temperature was used for Cd adsorption and desorption studies. For desorption experiment 10 successive desorptions were made for the whole range of initial Cd concentrations (20-300 microM) in the presence of 0.01 M Ca(NO3)2 or 0.03 M NaNO3 solutions. Cadmium adsorption was found to be higher in Na+ than Ca2+ probably due to the competition of Ca2+ ions with Cd2+ ions for adsorption sites on the surfaces of goethite. The effect of index cation on Cd adsorption diminished with increase in pH from 5.0 to 6.0. Cadmium desorption decreased with increase in pH from 5.0 to 6.0 in both Na and Ca systems. After 10 successive desorptions with 0.03 M NaNO3 at the lowest initially adsorbed Cd approximately 45%, 20% and 7% of the adsorbed Cd was desorbed at pH 5.0, 5.5 and 6.0, respectively. The corresponding desorptions in the presence of 0.01 M Ca(NO3)2 were 49%, 22% and 8%, respectively. The Freundlich parameter, k, based on each progressive step of desorption at different adsorbed concentration increased with increasing desorption step, which may indicates that a fraction of Cd was resistant to desorption. Low Cd desorbability from goethite may be due to its specific adsorption and/or possibly as a result of Cd entrapment in the cracks or defects in goethite structure.     

The role of Mn oxide doping in phosphate removal by Al-based bimetal oxides: adsorption behaviors and mechanisms

This study investigated the behaviors and mechanisms of phosphate adsorbed onto manganese (Mn) oxide-doped aluminum (Al) oxide (MODAO). The isotherm results demonstrated that the maximum amount of phosphorus (P) adsorbed onto MODAO was 59.8 mg/g at T?=?298 K (pH 6.0). This value was nearly twice the amount of singular AlOOH and could increase with rising temperatures. The kinetic results illustrated that most of the P was adsorbed onto MODAO within 5 h, which was shorter than the equilibrium time of phosphate adsorption onto AlOOH. The Elovich model effectively described the adsorption kinetic data of MODAO because of its heterogeneous surface. The optimal solution pH for phosphate removal was approximately 5.0 because of electrostatic interaction effects. Meanwhile, the decrease in P uptake with increasing ion strength suggested that phosphate adsorption occurred through an outer-sphere complex. Phosphates would compete for adsorption sites on the surface of MODAO in the presence of fluoride ion or sulfate. In addition, the spectroscopic analysis results of Fourier transform infrared spectroscopy and X-ray photoemission spectroscopy indicated that removal mechanisms of phosphate primarily include adhesion to surface hydroxyl groups and ligand exchange.     

In vitro biotransformation of PBDEs by root crude enzyme extracts: Potential role of nitrate reductase (NaR) and glutathione S-transferase (GST) in their debromination

In order to investigate the enzyme transformation of PBDEs and to track the key enzymes involved in PBDE degradation in plants, in vivo exposure of plants of ryegrass, pumpkin and maize and in vitro exposure of their root crude enzyme extracts to PBDEs were conducted. Degradation of PBDEs in the root crude enzyme solutions fit well with the first order kinetics (R² = 0.52–0.97, P < 0.05), and higher PBDEs degraded faster than the lower ones. PBDEs could be transformed to lower brominated PBDEs and hydroxylated-PBDEs by the root crude enzyme extracts with debromination as the main pathway which contributed over 90% of PBDE depletion. In vitro and in vivo exposure to PBDEs produced similar responses in root enzyme activities of which the nitroreductase (NaR) and glutathione-transferase (GST) activities decreased significantly, while the peroxidase, catalase and cytochrome P-450 activities had no significant changes. Furthermore, higher enzyme concentrations of NaR and GST led to higher PBDE debromination rates, and the time-dependent activities of NaR and GST in the root crude enzyme extracts were similar to the trends of PBDE depletion. All these results suggest that NaR and GST were the key enzymes responsible for PBDE degradation. This conclusion was further confirmed by the in vitro debromination of PBDEs with the commercial pure NaR and GST.     

Cadmium and lead bioavailability and their effects on polycyclic aromatic hydrocarbons biodegradation by spent mushroom substrate

Bioremediation of mixed metal–organic soil pollution constitutes a difficult task in different ecosystems all around the world. The aims of this work are to determine the capacity of two spent mushroom substrates (Agaricus bisporus and Pleurotus ostreatus) to immobilize Cd and Pb, to assess the effect of these metals on laccase activity, and to determine the potential of spent A. bisporus substrate to biodegrade four polycyclic aromatic hydrocarbons (PAH): fluorene, phenanthrene, anthracene, and pyrene, when those toxic heavy metals Cd and Pb are present. According to adsorption isotherms, spent P. ostreatus and A. bisporus substrates showed a high Pb and Cd adsorption capacity. Pb and Cd interactions with crude laccase enzyme extracts from spent P. ostreatus and A. bisporus substrates showed Cd and Pb enzyme inhibition; however, laccase activity of A. bisporus presented lower inhibition. Spent A. bisporus substrate polluted with PAH and Cd or Pb was able to biodegrade PAH, although both metals decrease the biodegradation rate. Spent A. bisporus substrate contained a microbiological consortium able to oxidize PAH with high ionization potential. Cd and Pb were immobilized during the bioremediation process by spent A. bisporus substrate. Consequently, spent A. bisporus substrate was adequate as a multi-polluted soil bioremediator.     

Characteristics of cadmium tolerance in 'Hermes' flax seedlings: contribution of cell walls

Most flax (Linum usitatissimum) varieties are described as tolerant to high concentrations of Cd. The aim of the present paper was to better characterize this tolerance, by studying the responses of flax plantlets, cv Hermes, to 18d growth on 0.5mM Cd. In Cd-treated seedlings, the majority of Cd was compartmentalized in the roots. Analysis of other elements showed that only Fe concentration was reduced, while Mn increased. Growth parameters of Cd treated flax were only moderately altered, with similar mass tolerance-indices for roots and shoots. Tissue anatomy was unaffected by treatment. The effect on lipid peroxidation, protein carbonylation and antioxidative activities appeared low but slightly higher in roots. The most important impacts of Cd were, in all organs, cell expansion, cell-wall thickening, pectin cross-linking and increase of cell-wall enzymatic activities (pectin methylesterase and peroxidase). Thus, the role of the cell wall in Cd tolerance might be important at two levels: (i) in the reinforcement of the tissue cohesion and (ii) in the sequestration of Cd.     

不同粒径土壤对氯丹的吸附性能及其急性毒性

以典型有机氯农药氯丹为研究对象,重点研究了不同粒径土壤颗粒对氯丹的吸附特性及其对发光菌急性毒性的影响。研究结果表明,不同粒径的土壤颗粒对氯丹的吸附性能依次为：粘粒（ 粗砂（200~2 000 μm）> 细砂（20~200 μm）。Freundlich等温吸附模型的线性相关系数最小为0.84,对不同粒径土壤吸附数据的拟合均优于Langmuir等温吸附模型。对吸附氯丹的吸附数据更符合准一级吸附动力学,其线性相关系数最高达到0.999。四种土壤颗粒浸出液对发光菌毒性的发光抑制率依次为细砂（-21%）≈粗砂（-21%）> 粘粒（-13%）> 粉粒（-9%）,即发光菌的急性毒性与土壤颗粒的吸附性能负相关。     

胶体迁移及其对典型类固醇雌激素的吸附

研究胶体自身的可迁移性和对污染物的可吸附性能够为地下环境中胶体对污染物的携带迁移作用提供重要依据。通过动态柱实验和静态批实验研究二氧化硅胶体、伊利石胶体和胡敏酸胶体在饱和多孔介质中的可迁移性以及对雌酮和雌二醇的吸附作用。结果表明：不同胶体在饱和多孔介质中的可迁移性有所差异,胡敏酸胶体和二氧化硅胶体分别在石英砂柱和河砂砂柱中迁移性最强,而伊利石胶体在2种多孔介质中的迁移性均较弱;准二级动力学模型对胶体吸附雌激素的数据拟合效果最好,吸附速率的控制因素可能包括表面吸附、化学络合等;Langmuir模型对胶体吸附雌激素的拟合效果较Freundlich模型更好,推测胶体对雌激素的吸附为单层吸附,3种胶体对雌酮和雌二醇的最大吸附量分别为90.09~3 333 mg?kg-1和116.28~2 000 mg?kg-1。因此,胶体的可迁移性和对雌激素的吸附作用能够为胶体影响雌激素在地下环境中的迁移提供理论指导。     

Transport and fate of dieldrin in poplar and willow trees analyzed by SPME

Dieldrin is a hydrophobic organochlorine insecticide that is persistent in the environment. The fate and transport of dieldrin in trees is important both in the context of potential remediation, as well as food chain impacts through dieldrin transport to shoots and leaves. Experiments were conducted to measure the degree of dieldrin partitioning to plant tissue and the potential for biodegradation of dieldrin in the microbe rich tree rhizosphere. Dieldrin was analyzed in water and plant tissue using headspace solid-phase microextraction (SPME) coupled with gas chromatography. Poplar and willow saplings planted in soil and watered with 10 microgl(-1) dieldrin for up to 9 months showed no adverse effects due to dieldrin exposure and no dieldrin was observed in plant shoots with a method detection limit (MDL) of 7 ngg(-1). One-week hydroponic tests of poplar saplings exposed to aqueous dieldrin also showed no detection of dieldrin in shoots, with an average of 66% of the dieldrin partitioned to the plant roots and an overall mass balance recovery of 76% in the plant-water system. The root concentration factor (RCF) was found to be 30+/-3 ml water g(-1) root. Biodegradation of dieldrin was not observed in an aqueous batch bioreactor containing 8 microgl(-1) dieldrin, nutrients and bacteria from the root zone of a poplar sapling that had been exposed to dieldrin for 9 months. These results show that planting trees is likely to be safe and potentially useful at sites containing low-levels of dieldrin in groundwater.     

Processing of aerogels and their applications toward CO2 adsorption and electrochemical reduction: a review

Environmental Science and Pollution Research - Aerogels are a unique class of nanoporous ultralight materials exhibiting wide range of textural characteristic properties and tunable porosities. Due...     

CTAB-HAP@ZMS复合材料的制备及其对氟离子的吸附性能

使用贝壳和粉煤灰等固体废弃物为原材料,采用水热合成法将十六烷基三甲基溴化铵(CTAB)改性后的羟基磷灰石(HAP)负载到粉煤灰基沸石分子筛(ZMS)上,得到一种高效的吸附剂(CTAB-HAP@ZMS)用于去除氟离子。当投加量为8.0 g·L⁻¹、pH为3、温度为55 ℃时,CTAB-HAP@ZMS复合材料的最高吸附容量达到了10.4 mg·g⁻¹,对10.0 mg·L⁻¹氟化钠溶液中F⁻的去除率可以达到95%。动力学和热力学拟合参数表明吸附过程主要为多分子层式、自发、吸热的化学吸附。将此吸附剂用于处理模拟地热水(F⁻初始浓度为8.0 mg·L⁻¹),去除率达到89%,残留浓度低于我国饮用水质量标准中F⁻的浓度限值(1.0 mg·L⁻¹)。此外,经4次循环再生吸附后,CTAB-HAP@ZMS复合材料仍然表现出较高的氟离子去除效率。该复合材料的制备不仅能使固体废物资源化,还在氟离子去除方面有广阔应用前景。     

Urban woodlands: their role in reducing the effects of particulate pollution

In recent years a substantial research effort has focused on the links between particulate air pollution and poor health. As a result the PM10 value has been set as a measure of such pollutants which can directly cause illness. Due to their large leaf areas relative to the ground on which they stand and the physical properties of their surfaces, trees can act as biological filters, removing large numbers of airborne particles and hence improving the quality of air in polluted environments. The role of vegetation and urban woodlands in reducing the effects of particulate pollution is reviewed here. The improvement of urban air quality achieved by establishing more trees in towns and cities is also illustrated.     

2种不同碱度钢渣及其负载HAP吸附镉的比较

为了探明低碱度钢渣、低碱度钢渣负载HAP(羟基磷灰石,hydroxyapatite)、高碱度钢渣和高碱度钢渣负载HAP 4种材料对水溶液中Cd²⁺的吸附特征,采用静态批实验的方法,分别从pH、反应时间和初始浓度等方面对其进行了考察;使用电镜扫描观察和X射线衍射分析等手段,运用吸附动力学模型、吸附等温线模型对吸附过程和吸附机理进行了分析与探讨。结果表明：4种材料对Cd²⁺的吸附效果顺序为高碱度钢渣负载HAP>高碱度钢渣>低碱度钢渣负载HAP>低碱度钢渣,其中低碱度钢渣及其负载HAP对Cd²⁺的吸附性能较差,且会发生脱附现象,不宜用作Cd²⁺的吸附材料;高碱度钢渣及其负载HAP对Cd²⁺的吸附性能较好,吸附过程均符合准二级吸附动力学模型和Langmuir吸附等温线模型;吸附过程主要为吸附剂表面上的单层化学吸附,吸附作用主要为离子交换作用和化学沉淀作用;此外,高碱度钢渣及其负载HAP对Cd²⁺最大吸附量分别为7.65 mg·g⁻¹和12.63 mg·g⁻¹,相比之下,提高了60.58%,这表明高碱度钢渣负载了HAP可大幅度提高其对Cd²⁺的吸附容量。钢渣碱度的差异性对其吸附镉的影响较大。