Trichoderma harzianum: a green sorbent for Pb(II) uptake from aqueous solutions

This investigation describes the use of specially cultivated, nonliving biomass of Trichoderma harzianum as a biosorbent for the batch removal of Pb(II) from a stirred system under different experimental conditions. The metal removal depended upon pH, sorbent particle size, initial Pb(II) concentration, shaking speed, and sorption time. The optimal experimental conditions for the removal of Pb(II) by T. harzianum with an initial metal concentration of 100 mg L^?1 were obtained at a particle size of 53 μm, a pH of 4.5, a shaking speed of 200 rpm, and a contact time of 720 min. The results were analyzed in terms of adsorption isotherms and kinetic models. The Freundlich isotherm model and pseudo second-order model fitted well in the data. T. harzianum proved to be a good biomaterial for accumulating Pb(II) from aqueous solutions (q = 460 mg g^?1).     

The performance of nitrate-reducing Fe(II) oxidation processes under variable initial Fe/N ratios: The fate of nitrogen and iron species

•Bacterially-mediated coupled N and Fe processes examined in incubation experiments. •NO₃⁻ reduction was considerably inhibited as initial Fe/N ratio increased. •The maximum production of N₂ occurred at an initial Fe/N molar ratio of 6. •Fe minerals produced at Fe/N ratios of 1–2 were mainly easily reducible oxides. The Fe/N ratio is an important control on nitrate-reducing Fe(II) oxidation processes that occur both in the aquatic environment and in wastewater treatment systems. The response of nitrate reduction, Fe oxidation, and mineral production to different initial Fe/N molar ratios in the presence of Paracoccus denitrificans was investigated in 132 h incubation experiments. A decrease in the nitrate reduction rate at 12 h occurred as the Fe/N ratio increased. Accumulated nitrite concentration at Fe/N ratios of 2–10 peaked at 12–84 h, and then decreased continuously to less than 0.1 mmol/L at the end of incubation. N₂O emission was promoted by high Fe/N ratios. Maximum production of N₂ occurred at a Fe/N ratio of 6, in parallel with the highest mole proportion of N₂ resulting from the reduction of nitrate (81.2%). XRD analysis and sequential extraction demonstrated that the main Fe minerals obtained from Fe(II) oxidation were easily reducible oxides such as ferrihydrite (at Fe/N ratios of 1–2), and easily reducible oxides and reducible oxides (at Fe/N ratios of 3–10). The results suggest that Fe/N ratio potentially plays a critical role in regulating N₂, N₂O emissions and Fe mineral formation in nitrate-reducing Fe(II) oxidation processes.     

Application of permanganate in the oxidation of micropollutants: a mini review

As a green oxidant, permanganate has received considerable attention for the removal of micropollutants in drinking water treatment. To provide a better understanding of the oxidation of organic micropollutants with permanganate, the oxidation kinetics of 32 micropollutants were compiled. The pollutants include algal toxins, endocrine disrupting chemicals (EDCs), and pharmaceuticals. The oxidation kinetics of micropollutants by permanganate were found to be first order with respect to both contaminant and permanganate concentrations from which second-order rate constants (k″) were obtained. Permanganate oxidized the heterocyclic aromatics with vinyl moiety (i.e., microcystins, carbamazepine, and dichlorvos) by the addition of double bonds. For the polycyclic aromatic hydrocarbons (PAHs) with alkyl groups, permanganate attacked the benzylic C-H through abstraction of hydrogen. The mechanism for the oxidation of phenolic EDCs by permanganate was a single electron transfer and aromatic ring cleavage. The presence of background matrices could enhance the oxidation of some phenolic EDCs by permanganate, including phenol, chlorinated phenols, bisphenol A, and trichlosan. The toxicity of dichlorvos solution increased after permanganate oxidation, and the estrogenic activity of bisphnol A/estrone increased significantly at the beginning of permanganate oxidation. Therefore, the toxicity of degradation products or intermediates should be determined in the permanganate oxidation processes to better evaluate the applicability of permanganate. The influence of background ions on the permanganate oxidation process is far from clear and should be elucidated in the future studies to better predict the performance of permanganate oxidation of micropollutants. Moreover, methods should be employed to catalyze the permanganate oxidation process to achieve better removal of micropollutants.     

Microbial electrolysis cells with biocathodes and driven by microbial fuel cells for simultaneous enhanced Co(II) and Cu(II) removal

Cobalt and copper recovery from aqueous Co(II) and Cu(II) is one critical step for cobalt and copper wastewaters treatment. Previous tests have primarily examined Cu(II) and Co(II) removal in microbial electrolysis cells (MECs) with abiotic cathodes and driven by microbial fuel cell (MFCs). However, Cu(II) and Co(II) removal rates were still slow. Here we report MECs with biocathodes and driven by MFCs where enhanced removal rates of 6.0±0.2 mg?L⁻¹?h⁻¹ for Cu(II) at an initial concentration of 50 mg?L⁻¹ and 5.3±0.4 mg?L⁻¹ h⁻¹ for Co(II) at an initial 40 mg?L⁻¹ were achieved, 1.7 times and 3.3 times as high as those in MECs with abiotic cathodes and driven by MFCs. Species of Cu(II) was reduced to pure copper on the cathodes of MFCs whereas Co(II) was removed associated with microorganisms on the cathodes of the connected MECs. Higher Cu(II) concentrations and smaller working volumes in the cathode chambers of MFCs further improved removal rates of Cu(II) (115.7 mg?L⁻¹?h⁻¹) and Co(II) (6.4 mg?L⁻¹?h⁻¹) with concomitantly achieving hydrogen generation (0.05±0.00 mol?mol⁻¹ COD). Phylogenetic analysis on the biocathodes indicates Proteobacteria dominantly accounted for 67.9% of the total reads, followed by Firmicutes (14.0%), Bacteroidetes (6.1%), Tenericutes (2.5%), Lentisphaerae (1.4%), and Synergistetes (1.0%). This study provides a beneficial attempt to achieve simultaneous enhanced Cu(II) and Co(II) removal, and efficient Cu(II) and Co(II) wastewaters treatment without any external energy consumption.     

Effect Of pH on the complexation of U(II) with organic matter dissolved in resh waters

In the present work we study the effect of pH on the complexation of copper with organic matter dissolved in fresh surface waters. Samples collected in rivers of Galicia (NW of Spain) were titrated with copper solution at pH values in the range 5.5–7.5. Copper concentration was measured by DPASV technique. The complexation parameters were obtained from the simple model of 1 : 1 complex formation. The obtained values show a linear increase of the logarithm of the conditional stability constant as the pH increases.     

Role of Acinetobacter sp. in arsenite As(III) oxidation and reducing its mobility in soil

Microbial arsenite oxidation was observed by Acinetobacter sp. XS21, this strain oxidised arsenite As(III) up to 80?mM within 48–72?h of incubation. The present strain XS21 oxidised As(III) at a very high concentration in a shorter interval of time than any of the previous reported microbes. Further, XS21 was applied to the soil to observe its ability in reducing the mobility of As(III), and we found that Acinetobacter sp. XS21 efficiently removed arsenite from soluble-exchangeable fraction and removed 70% of the arsenite as compared to control. This feature makes it a potential candidate for bioremediation. Arsenic-resistant bacteria with strong As(III)-oxidising ability may have potential to improve bioremediation of As(III)-contaminated sites. To understand their basis of resistance and transformation we found the As(III) oxidase gene using degenerate primer and amplified ～550?bp of aioA gene. Amplified aioA gene sequence exhibiting 52% identity in terms of gene and deduced protein sequence to Uncultured bacterium, and Achromobacter sp. arsenite oxidase of larger subunit. Arsenite oxidase, an enzyme, was also observed in this isolate, which may provide a resistance and transforming ability. This bacterium was identified as Acinetobacter sp., by sequencing 16s rRNA gene sequence analysis.     

Soil lead (Pb) in residential transects through Lubbock,Texas: a preliminary assessment

Residential lead (Pb) contamination, resulting from decades-long use of leaded gasoline and lead-based paint, is likely to be present in soils in most urban areas. A screening level sampling effort demonstrated that Lubbock, Texas, USA, like other cities of its age and size, has areas of elevated soil Pb. This effort was based on soil sampling performed on residential, commercial and thoroughfare properties. The focus of this study was to investigate that component of soil contamination due to combustion of leaded gasoline. Soils were collected from the 1–2 cm surface layer from street-side property borders, well away from buildings that might lead to soil contamination from leaded paint chips. All samples were analyzed for Pb after a 1 M HNO₃ mild extraction to determine the amount of bioavailable Pb. Two of three transects through the city demonstrated significant trends of decreasing Pb concentrations with distance from the city center, paralleling a decrease in developed property age. Peak soil Pb concentrations outside city development was 4.9 ± 0.6 mg/kg while the median concentration for the city was 35.4 mg/kg. Peak soil Pb concentrations in the city center ranged from 90.0 to 174.0 mg/kg and decreased exponentially to 6.0–9.0 mg/kg at the furthest terminus of the residential transects.     

Geometry of Zn(II) complexes with dissolved organic matter: X-ray studies at variable pH

The structure of Zn(II) complexes with dissolved organic matter (DOM) is an important consideration in developing molecular-level models of Zn(II) speciation, but recent reports favoring the tetrahedral geometry differ from earlier findings that geometry was largely octahedral. In general, the presence of thiolate ligands favors the tetrahedral geometry, while O and N ligands favor the octahedral geometry. This work presents extended X-ray absorption fine structure (EXAFS) and X-ray absorption near-edge structure (XANES) spectroscopic results, indicating an octahedral geometry over the pH range of 5–9 for a freshwater DOM isolate. Changes in XANES derivatives as a function of pH can be explained in terms of ligand protonation and/or changing ligand groups. Tetrahedral Zn(II)–DOM geometry may be restricted to binding environments containing thiol groups.     

Influence of complexation on lead(II) and cadmium(II) percolation through a clay liner

Wastes are usually stocked in waste disposals without any pre-treatment. Runoff waters lead to the formation of leachates containing mineral and organic pollutants. In order to prevent groundwater contamination, a double barrier is placed on the landfill bottom. The first one is an active barrier made up of a draining system and a geomembrane, and the second one, consisting of a clay liner allowing pollutant retention, is considered as a passive system. The aim of this work is to evaluate the complexation impact on the organic and inorganic retention. Percolations on columns filled with clay are performed, which allow a better knowledge of the transfer of metallic pollutants, complexed or not, through a model porous media, considering charge and conditional stability of complexes.     

含氮有机污染物在超临界水氧化(SCWO)中去除的QSAR模型

超临界水氧化(SCWO)作为一项高效的去除水体中有机污染物的技术已得到了广泛的应用.为了更好地理解含氮有机物污染物在SCWO中总氮(TN)去除的规律,本研究以定量构效关系(QSAR)模型为方法,构建了41种含氮有机污染物在SCWO中TN％与有机污染物分子量子化学参数之间的QSAR模型.其最优QSAR模型结果为TN％=8...     

铅（Pb^2＋）致高血压大鼠胸主动脉病变的相关基因及信号转导途径

采用表达芯片研究铅(Pb2+)致高血压大鼠模型病变主动脉的基因表达谱,以及可能涉及的信号转导途径.结果表明,Pb2+致高血压大鼠和对照组相比,在3463个已知基因和表达序列标签(EST)中,有24个基因和1个EST表达上调幅度≥2倍;有2个基因和1个EST表达下调幅度≥2倍.在差异表达≥2倍的26个基因中,有13个上调的基因与细胞凋亡、局部粘附、细胞生长、增殖、细胞迁移、平滑肌兴奋、胶原重构等生物学过程相关;2个下调基因与能量代谢有关.表达差异基因相对集中的信号途径是与细胞运动、增殖和存活关系密切的局部粘附信号途径.     

Effects of Cr(III) organic compounds on Lactobacillus plantarum

Biotransformation of Cr(VI) to less toxic Cr(III) has been known to produce insoluble Cr(III) compounds and soluble Cr(III) organic complexes. However, recent research reports have indicated that Cr(III) organic complexes are relatively stable in the environment. Little has been reported on the fate and toxic effects of Cr(III) organic compounds on organisms. In this study, the toxic effects of the soluble Cr(III) organic complexes [Cr(III) citrate, Cr(III) histidine, Cr(III) lactate and Cr(III) glutamate] to a local strain of Lactobacillus plantarum isolated from sauerkraut was investigated. Growth inhibition, viable cell count and lactic acid inhibition were measured to determine the toxicity potential of the test compounds. The EC₅₀ values of Cr(III) citrate, Cr(III) histidine, Cr(III) lactate, and Cr(III) glutamate, calculated from the percent growth inhibition were found to be 56 mg L^?1, 70 mg L^?1, 81 mg L^?1, and 85 mg L^?1, respectively. Similar trend was observed in the viable cell counts and lactic acid production. Cr(VI) was observed to be more toxic than the Cr(III) organic compounds, while inorganic Cr(III) was the least toxic. The severity seemed to increase with increase in chromium compounds’ concentration. The results showed that Cr(III) citrate was the most toxic Cr(III) organic compound, while Cr(III) glutamate was the least.     

多壁碳纳米管存在环境下Pb、Zn对斑马鱼毒性的变化(The Change of the Toxicity of Pb and Zn on Zebrafish in the Case of the Existence of Multi-Walled Carbon Nanotubes)

研究了重金属铅、锌对斑马鱼的急性毒性效应及在人工碳纳米材料——多壁碳纳米管存在环境下,铅、锌对斑马鱼毒性的变化.结果显示,随着铅(Pb(NO3)2)、锌(ZnSO4)浓度的增加以及染毒时间的延长,斑马鱼死亡率逐渐增加;单一多壁碳纳米管悬液(10mg·L-1)对斑马鱼无明显毒性效应.Pb和Zn对斑马鱼24h、48h和96h的LC50分别为5.38mg·L-1、3.99mg·L-1、3.83mg·L-1和26.37mg·L-1、21.39mg·L-1、20.62mg·L-1;在多壁碳纳米管存在条件下,二者对斑马鱼24h、48h和96h的LC50分别为2.74mg·L-1、2.26mg·L-1、2.15mg·L-1和21.85mg·L-1、17.17mg·L-1、16.77mg·L-1.多壁碳纳米管存在条件下铅、锌对斑马鱼的LC50显著降低,提示碳纳米材料可能会增加重金属对水生生物的毒性.     

Removal of pentachlorophenol from contaminated soil by catalytic oxidation with iron(III)-porphyrin complexes and potassium monopersulfate

Pentachlorophenol (PCP) in contaminated soil was removed by treatment with aqueous solutions of iron(III)-porphyrin complexes as catalysts and potassium monopersulfate (KHSO₅) as the oxygen donor. The contaminated soils were artificially prepared by spiking PCP to the kaolin and ando soils. Three types of iron(III)-porphyrin complexes, tetra(?p-sulfophenyl) porphineiron(III) (Fe(III)-TPPS), tetra(N-methyl-4-pyridil)porphineiron(III) (Fe(III)-TMPyP) and heme, were examined, and Fe(III)-TPPS was found to be the most effective for removing PCP. Although the sequential addition of KHSO₅ was examined, in an attempt to improve the efficiency of PCP removal, it was not effective. In a preliminary test of various aqueous solutions, the addition of humic acid (HA), with a lower degree of humification, led to a significant enhancement in PCP removal. When HA was added to the soil system, the percentages of PCP removal were increased by up to 10% compared to the absence of HA. Therefore, the addition of HA to the catalytic system was useful in enhancing PCP removal from contaminated soil.     

Removal of cadmium(II), lead(II), and chromium(VI) ions from aqueous solution using clay

Removal of cadmium(II), lead(II), and chromium(VI) from aqueous solution using clay, a naturally occurring low-cost adsorbent, under various conditions, such as contact time, initial concentration, temperature, and pH has been investigated. The sorption of these metals follows both Langmuir and Freundlich adsorption isotherms. The magnitude of Langmuir and Freundlich constants at 30°C for cadmium, lead, and chromium indicate good adsorption capacity. The kinetic rate constants (K _ad) indicate that the adsorption follows first order. The thermodynamic parameters: free energy change (ΔG ^o), enthalpy change (ΔH ^o), and entropy change (ΔS ^o) show that adsorption is an endothermic process and that adsorption is favored at high temperature. The results reveal that clay is a good adsorbent for the removal of these metals from wastewater.     

Fenton法降解水中布洛芬

采用Fenton法降解水中布洛芬,考察了H2O2投加量、FeSO.47H2O与H2O2的比值、初始pH、反应时间等因素对布洛芬去除率的影响,通过正交实验确定影响作用大小依次为:[Fe2+]∶[H2O2]的物质的量之比>H2O2的投加量>pH值,最佳的反应工艺条件为:H2O2的投加量为3 mL.L-1,[Fe2+]∶[H2O2]的物质的量之比为1∶10,反应初始pH值为3,反应时间为40 min.在最佳条件下布洛芬的去除率达到86%以上.同时对布洛芬降解反应动力学进行了研究,发现Fenton降解布洛芬符合二级反应动力学规律.     

Effects of oxidizing environment on digestate humification and identification of substances governing the dissolved organic matter (DOM) transformation process

• Liquid digestate humification was investigated under different oxidizing environment. • Tryptophan-like substances dominated the transformation of the liquid digestate DOM. • The humification sequence of the liquid digestate DOM was identified. • UV₃₂₅ was first identified as a pre-humus intermediate during humification reaction. The formation of humic-like acids (HLAs) is an essential process for converting liquid digestate into organic soil amendments to enhance agricultural sustainability. The aim of this study was to investigate the impact of oxygen and/or MnO₂ on the production of HLAs. Herein, abiotic humification performance of the digestate dissolved organic matter (DOM) is investigated with fluxes of air and N₂ in the absence and presence of MnO₂. Our results demonstrated that the fate of digestate DOM greatly depends on the oxidizing environment, the MnO₂ enhanced nitrogen involved in the formation of HLAs. The synergistic effects of MnO₂ and oxygen effectively improved the production of HLAs, and the corresponding component evolution was analyzed using spectroscopic evidence. The two-dimensional correlation spectroscopy results demonstrated that the reaction sequence of digestate DOM followed the order of protein-like substances, substances with an absorbance at 325 nm, substances with UV absorbance at 254 nm and HLAs. Additionally, excitation emission matrix fluorescence combined with parallel factor analysis (EEM-PARAFAC) showed that tryptophan-like C3 was more prone to transformation than tyrosine-like C2 and was responsible for the humification process. The substance with an absorbance at 325 nm was a reaction intermediate in the transformation process of protein-like substances to HLAs. The above findings can be used to promote the production of liquid fertilizer associated with carbon sequestration as well as the sustainable development of biogas production.     

Decomposition of aqueous chlorinated contaminants by UV irradiation with H2O2

In the present study, the decomposition rates of carbon tetrachloride (CCl₄) and 2,4-dichlorophenol (2,4-DCP) in water by the ultraviolet (UV) light irradiation alone and H₂O₂/UV were experimentally investigated. The detailed experimental studies have been conducted for examining treatment capacities of the two different ultraviolet light sources (low and medium pressure Hg arc) in H₂O₂/UV processes. The low or medium UV lamp alone resulted in a 60%–90% decomposition of 2,4-DCP while a slight addition of H₂O₂ resulted in a drastic enhancement of the 2,4-DCP decomposition rate. The decomposition rate of 2,4-DCP with the medium pressure UV lamp alone was about 3–6 times greater than the low pressure UV lamp alone. In the direct photolysis of aqueous CCl₄, the medium pressure UV lamp had advantage over the low pressure UV lamp because the molar extinction coefficient of CCl₄ at shorter wavelength (210–220 nm) is about 20 to 50 times higher than that at 254 nm. However, adding H₂O₂ to the medium pressure UV lamp system rendered a negative oxidation rate because H₂O₂ acted as a UV absorber being competitive with CCl₄ due to negligible reaction between CCl₄ and OH radicals. The results from the present study indicated significant influence of the photochemical properties of the target contaminants on the photochemical treatment characteristics for designing cost-effective UV-based degradation of toxic contaminants.     

应用生物配体模型研究铅和镉及其混合物联合毒性

为探讨生物配体模型(BLM)对金属混合物的适用性,以莱茵衣藻(Chlamydomonas reinhardtii)为研究对象,以藻体内短时间(≤60 min)生物积累量为指标,研究了Pb和Cd对莱茵衣藻的联合毒性作用。结果表明:Pb和Cd单独暴露下,藻体内生物积累过程可用米门方程(Michaelis-Menten equation)来描述。计算得到Cd传输位点的最大吸收通量Jmax为(8.312±0.034)×10-12mol·cm-2·s-1,该位点的半饱和系数(米门系数)KM=(1.012±0.032)×10-6mol·L-1,稳定常数KCd=0.988×106(mol·L-1)-1;Pb传输位点的Jmax为(1.28±0.039)×10-11mol·cm-2·s-1,该位点的KM=(3.56±0.34)×10-7mol·L-1,KPb为2.81×106(mol·L-1)-1。Cd和Pb的竞争实验中,当固定Cd的浓度,其吸收通量随Pb的增加而显著降低;固定Pb的浓度,其吸收通量随Cd的增加略有降低。这表明Pb和Cd可能存在相同的传输位点,且Pb对传输位点的结合能力要远大于Cd。在低浓度Pb和Cd的混合暴露溶液中,短时间内绿藻对Pb的生物积累量会远大于Cd。研究结果表明BLM可用于描述低浓度下Cd和Pb的竞争关系。     

Fluorescence studies of dye displacement from DNA by chromium(III) complexes: Evidence for cation induced DNA condensations

The interactions of 10 different chromium(III) complexes with isolated calf thymus DNA have been analysed by studying the electronic and fluoresence spectra of intercalated ethidiumbromide. Triply charged cationic complexes including: [Cr(urea)₆]Cl₃.3H₂O, [Cr(1,10‐phenanthroline)₃](ClO₄)₃.2H₂O, [Cr(2,2'‐bipyridyl)₃] (ClO₄)₃.2H₂O, [Cr(ethylendiamine)₃]Cl₃.3.5H₂O and [Cr(NH₃)₆](NO₃)₃ displaced the dye from DNA. Similar effects were observed in experiments using the non‐intercalating dye bisbenzimidazole ("Hoechst 33258"). However, singly charged cationic, anionic and uncharged chromium(III) complexes such as: cis‐[Cr(1,10‐phenanthroline)₂Cl₂]Cl.2H₂O, cis‐[Cr(2,2'‐bipyridyl)₂Cl₂]Cl.2H₂O, [Cr(glutathione)₂]Na₂, [Cr(cysteine)₂]Na.2H₂O and [Cr(glycine)₃] were unable to displace both ethidiumbromide and bisbenzimidazole from DNA. There was no evidence for the formation of co‐ordinate bonds between chromium(III) and DNA for any of the above complexes. The charge and type of ligand are important in controlling the interaction of chromium(III) with isolated DNA in vitro. Our findings indicate that the outer sphere interaction of a chromium(III) complex with DNA is weak and unlikely to be the mechanism by which chromate causes DNA impairments in vivo and in vitro.