Copper (II) adsorption by the extracellular polymeric substance extracted from waste activated sludge after short-time aerobic digestion

The extracellular polymeric substance (EPS) extracted from waste activated sludge (WAS) after short-time aerobic digestion was investigated to be used as a novel biosorbent for Cu²⁺ removal from water. The EPS consisted of protein (52.6 %, w/w), polysaccharide (30.7 %, w/w), and nucleic acid (16.7 %, w/w). Short-time aerobic digestion process of WAS for about 4 h promoted the productivity growth of the EPS for about 10 %. With a molecular weight of about 1.9?×?10⁶ Da, the EPS showed a linear structure with long chains, and contained carboxyl, hydroxyl, and amino groups. The sorption kinetics was well fit for the pseudo-second-order model, and the maximum sorption capacity of the EPS (700.3 mg Cu²⁺/g EPS) was markedly greater than those of the reported biosorbents. Both Langmuir model and Freundlich model commendably described the sorption isotherm. The Gibbs free energy analysis of the adsorption showed that the sorption process was feasible and spontaneous. According to the complex results of multiple analytical techniques, including scanning electron microscopy, Fourier transform infrared spectroscopy, atomic force microscopy, etc., the adsorption process took place via both physical and chemical sorption, but the electrostatic interaction between sorption sites with the functional groups and Cu²⁺ is the major mechanism.     

Metal binding properties of extracellular polymeric substances extracted from anaerobic granular sludges

Extracellular polymeric substances (EPS) were extracted from four anaerobic granular sludges with different procedures to study their involvement in biosorption of metallic elements. EPS extracts are composed of closely associated organic and mineral fractions. The EPS macromolecules (proteins, polysaccharides, humic-like substances, nucleic, and uronic acids) have functional groups potentially available for the binding of metallic elements. The acidic constants of these ionizable groups are: pK _a1 (4–5) corresponding to the carboxyl groups; pK _a2 (6–7) corresponding to the phosphoric groups; pK _a3 (8–10) and pK _a4 (≈10) corresponding to the phenolic, hydroxyl, and amino groups. The polarographic study confirms the higher affinity of the EPS to bind to lead than to cadmium. Moreover, the binding of these metallic compounds with the EPS is a mix of several sorption mechanisms including surface complexation, ion exchange, and flocculation. Inorganic elements were found as ions linked to organic molecules or as solid particles. The mineral fraction affects the binding properties of the EPS, as the presence of salts decreases the EPS binding ability. Calcite and apatite particles observed on SEM images of EPS extracts can also sorb metallic elements through ion exchange or surface complexation.     

Sorption of cyromazine on humic acid: Effects of pH,ionic strength and foreign ions

Cyromazine (CY) is a triazine pesticide used as an insect growth inhibitor for fly control in cattle manure, field crops, vegetables, and fruits. Sorption of CY onto humic acid (HA) may affect its environmental fate. In this study, HA was used to investigate the sorption of CY at different solution chemistry conditions (pH, ionic strength) and in the presence of foreign ions and norfloxacin. All sorption isotherms fitted well with the Freundlich and Langmuir models. The sorption reached a maximum at initial pH 4.0 over the initial pH range of 3.0–7.0, implying that the primary sorption mechanism was cation exchange interaction between CY⁺ species and the negatively charged functional groups of HA. Increasing Ca²⁺ concentration resulted in a considerable reduction in the K _d values of CY, hinting that Ca²⁺ had probably competed with CY⁺ for the cation exchange sites on the surfaces of HA. The sorption of CY on HA in different ionic media followed the order of NH₄Cl ≈ KCl > K₂SO₄ > ZnCl₂ ≈ CaCl₂ at pH 5.0. Spectroscopic evidence demonstrated that the amino groups and triazine ring of CY was responsible for sorption onto HA, while the carboxyl group and the O-alkyl structure of HA participated in adsorbing CY.     

Preparation of lactic acid modified cellulose nanoparticles by microwave heating for preconcentration of copper from blood and food samples

In this study, nano-sized cellulose modified with lactic acid (MW-Ce-LA) was prepared with the assistant of microwave then used for the adsorption of Cu²⁺ from real samples. This modified cellulose was characterized by means of FTIR, TEM, XRD, and elemental analysis. ICP-OES was used for determination of Cu²⁺. The effect of pH, adsorption times, temperature, sorbent dose, and initial adsorbate concentration were studied to detect the ideal adsorption condition. Langmuir model proved to be the best to fit the adsorption isotherm experiments with maximum adsorption capacity of 90.3 mg g^?1 Cu²⁺. Calculated thermodynamic parameters (ΔG° and ΔH°) for adsorption of Cu²⁺ on MW-Ce-LA suggested exothermic and nonspontaneous character of the adsorption process. The reusability tests indicated regeneration of the prepared adsorbent simply using 1 mol L^?1 of HCl. The examined method was used effectively to preconcentrate Cu²⁺ from water, blood, and food samples.

     

Photoinductive activity of humic acid fractions with the presence of Fe(III): the role of aromaticity and oxygen groups involved in fractions

Relationship between the photoinductive activity and the properties of humic acids (HA) fractions were investigated with and without Fe(III). Three fractions were separated based on the molecular weight (M(w)) and were obtained following the order of M(w): F(A)>F(B)>F(C). Compared to F(A) and F(B), photodegradation of atrazine under simulated sunlight was much faster in solution containing F(C), whose structure was dominated by greater aromaticity, more oxygen groups and fluorophores. The interaction of HA fractions and Fe(III) was studied using fluorescence spectrometry and F(C) had the largest quenching constant. The capacity of electron transfer, estimated from the amount of photoformed Fe(II), was also highest for F(C). Thus, the Fe(III)-F(C) complex was efficient in phototransformation of atrazine in nearly neutral aqueous solutions. These results suggest that the aromaticity and oxygen groups content of HA exert great influence on the binding ability of metals and on the fate of pollutants in natural waters.     

Growth and metal removal potential of a Phormidium bigranulatum-dominated mat following long-term exposure to elevated levels of copper

The present study explores the tolerance and metal removal response of a well-developed 2-week-old Phormidium mat after long-term exposure to Cu²⁺-enriched medium. Cu²⁺ enrichment inhibited increase in mat biomass in a concentration-dependent manner. Mat area and the number of entrapped air bubbles decreased as Cu²⁺ concentration increased in the medium. Decrease in number of air bubbles obviously reflects the adverse effect of Cu²⁺ on photosynthetic performance of the mat. Metal enrichment did not substantially alter the amount of pigments, such as chlorophyll a, chlorophyll b, carotenoids, and phycocyanin, in the mat. Enhancement of Cu²⁺ concentration in the medium led to changes in species composition of the test mat; however, Phormidium bigranulatum always remained the dominant organism. Relative share of green algae and some cyanobacterial taxa, namely, Lyngbya sp. and Oscillatoria tenuis, in the mat were increased by Cu²⁺ enrichment. The mat successfully removed 80 to 94 % Cu²⁺ from the growth medium containing 10 to 100 μM Cu²⁺. Extracellular polysaccharides, whose share increased in the mat community after metal addition, seem to have contributed substantially to metal binding by the mat biomass.     

Antifungal activities against toxigenic Fusarium specie and deoxynivalenol adsorption capacity of ion-exchanged zeolites

Zeolites are often used as adsorbents materials and their loaded cations can be exchanged with metal ions in order to add antimicrobial properties. The aim of this study was to use the 4A zeolite and its derived ion-exchanged forms with Zn²⁺, Li⁺, Cu²⁺ and Co²⁺ in order to evaluate their antifungal properties against Fusarium graminearum, including their capacity in terms of metal ions release, conidia germination and the deoxynivalenol (DON) adsorption. The zeolites ion-exchanged with Li⁺, Cu²⁺, and Co²⁺ showed an excellent antifungal activity against F. graminearum, using an agar diffusion method, with a zone of inhibition observed around the samples of 45.3 ± 0.6 mm, 25.7 ± 1.5 mm, and 24.7 ± 0.6 mm, respectively. Similar results using agar dilution method were found showing significant growth inhibition of F. graminearum for ion-exchanged zeolites with Zn²⁺, Li⁺, Cu²⁺, and Co²⁺. The fungi growth inhibition decreased as zeolite-Cu²⁺>zeolite-Li⁺>zeolite-Co²⁺>zeolite-Zn²⁺. In addition, the conidia germination was strongly affected by ion-exchanged zeolites. With regard to adsorption capacity, results indicate that only zeolite-Li⁺ were capable of DON adsorption significantly (P < 0.001) with 37% at 2 mg mL^?1 concentration. The antifungal effects of the ion-exchanged zeolites can be ascribed to the interactions of the metal ions released from the zeolite structure, especially for zeolite-Li⁺, which showed to be a promising agent against F. graminearum and its toxin.     

Synthesis and characterization of magnetic Fe3O4@CaSiO3 composites and evaluation of their adsorption characteristics for heavy metal ions

A two-component material (Fe₃O₄@CaSiO₃) with an Fe₃O₄ magnetite core and layered porous CaSiO₃ shell from calcium nitrate and sodium silicate was synthesized by precipitation. The structure, morphology, magnetic properties, and composition of the Fe₃O₄@CaSiO₃ composite were characterized in detail, and its adsorption performance, adsorption kinetics, and recyclability for Cu²⁺, Ni²⁺, and Cr³⁺ adsorption were studied. The Fe₃O₄@CaSiO₃ composite has a 2D core–layer architecture with a cotton-like morphology, specific surface area of 41.56 m²/g, pore size of 16 nm, and pore volume of 0.25 cm³/g. The measured magnetization saturation values of the magnetic composite were 57.1 emu/g. Data of the adsorption of Cu²⁺, Ni²⁺, and Cr³⁺ by Fe₃O₄@CaSiO₃ fitted the Redlich–Peterson and pseudo-second-order models well, and all adsorption processes reached equilibrium within 150 min. The maximum adsorption capacities of Fe₃O₄@CaSiO₃ toward Cu²⁺, Ni²⁺, and Cr³⁺ were 427.10, 391.59, and 371.39 mg/g at an initial concentration of 225 mg/L and a temperature of 293 K according to the fitted curve with the Redlich–Peterson model, respectively. All adsorption were spontaneous endothermic processes featuring an entropy increase, including physisorption, chemisorption, and ion exchange; among these process, chemisorption was the primary mechanism. Fe₃O₄@CaSiO₃ exhibited excellent adsorption, regeneration, and magnetic separation performance, thereby demonstrating its potential applicability to removing heavy metal ions.

     

Nonlinear binding of phenanthrene to the extracted fulvic acid fraction in soil in comparison with other organic matter fractions and to the whole soil sample

Fractions of soil organic matter in a natural soil were extracted and sorption (or binding) characteristics of phenanthrene on each fraction and to the whole sample were investigated. The organic carbon normalized single point sorption (or binding) coefficient followed lipid > humin (HM) > humic acid (HA) > fulvic acid (FA) > whole soil sample, while the nonlinear exponent exhibited lipid > FA > HA > whole soil sample > HM. FA showed nonlinear binding of phenanthrene as it often does with other fractions. HM and HA contributed the majority of organic carbon in the soil. The calculated sorption coefficients of the whole soil were about two times greater than the measured values at different equilibrium phenanthrene concentrations. As for phenanthrene, the sorption capacity and nonlinearity of the physically mixed HA-HM mixtures were stronger as compared to the chemically reconstituted HA-HM composite. This was attributed to (besides the conditioning effect of the organic solvents) interactions between HA and HM and acid-base additions during fractionation.     

Simultaneous adsorption and degradation of Zn2+ and Cu2+ from wastewaters using nanoscale zero-valent iron impregnated with clays

Clays such as kaolin, bentonite and zeolite were evaluated as support material for nanoscale zero-valent iron (nZVI) to simultaneously remove Cu²⁺ and Zn²⁺ from aqueous solution. Of the three supported nZVIs, bentonite-supported nZVI (B-nZVI) was most effective in the simultaneous removal of Cu²⁺ and Zn²⁺ from a aqueous solution containing a 100 mg/l of Cu²⁺ and Zn²⁺, where 92.9 % Cu²⁺ and 58.3 % Zn²⁺ were removed. Scanning electronic microscope (SEM) revealed that the aggregation of nZVI decreased as the proportion of bentonite increased due to the good dispersion of nZVI, while energy dispersive spectroscopy (EDS) demonstrated the deposition of copper and zinc on B-nZVI after B-nZVI reacted with Cu²⁺ and Zn²⁺. A kinetics study indicated that removing Cu²⁺ and Zn²⁺ with B-nZVI accorded with the pseudo first-order model. These suggest that simultaneous adsorption of Cu²⁺and Zn²⁺ on bentonite and the degradation of Cu²⁺and Zn²⁺ by nZVI on the bentonite. However, Cu²⁺ removal by B-nZVI was reduced rather than adsorption, while Zn²⁺ removal was main adsorption. Finally, Cu²⁺, Zn²⁺, Ni²⁺, Pb²⁺ and total Cr from various wastewaters were removed by B-nZVI, and reusability of B-nZVI with different treatment was tested, which demonstrates that B-nZVI is a potential material for the removal of heavy metals from wastewaters.     

Kinetics and equilibrium properties of the biosorption of Cu2+ by algae

The purpose of this study was to examine the kinetics and equilibrium properties of freshwater algae with Cu²⁺. This was a model system to explore using algae as biosensors for water quality. Methods included making luminescence measurements (fluorescence) and copper ion-selective electrode (CuISE) measurements vs. time to obtain kinetic data. Results were analyzed using a pseudo-first-order model to calculate the rate constants of Cu²⁺ uptake by algae: k _p(Cu?Calgae)?=?0.0025?±?0.0006?s^?1 by CuISE and k _p(Cu?Calgae)?=?0.0034?±?0.0011?s^?1 by luminescence. The binding constant of Cu?Calgae, K _Cu?Calgae, was 1.62?±?0.07?×?10⁷?M^?1. Fluorescence results analyzed using the Stern?CVolmer relationship indicate that algae have two types of binding sites of which only one appears to affect quenching. The fluorescence-based method was found to be able to detect the reaction of algae with Cu²⁺ quickly and at a detection limit of 0.1?mg?L^?1.     

In vitro effects of various xenobiotics on Fusarium spp. strains isolated from cereals

This study aimed to determine the susceptibility of Fusarium spp. strains isolated from cereals to selected heavy metals, fungicides and silver nanoparticles. The experiments were conducted using 50 Fusarium strains belonging to five species: F. graminearum, F. culmorum, F. oxysporum, F. sporotrichioides and F. avenaceum. The strains were found to be highly resistant to Pb²⁺ and Zn²⁺. Medium resistance to Cu²⁺ and Mn²⁺ and low resistance to Cd²⁺ and Fe³⁺ was also observed. Among the tested fungicides, formulations containing azoxystrobin, prochloraz and tebuconazole proved to be the most effective in inhibiting the growth of fungi, as they affected fungal growth in each of the applied doses. Susceptibility of Fusarium spp. to nanosilver, demonstrated in this study, shows the legitimacy of using nanostructures as fungicidal agents. The results confirm high diversity of the analyzed fungal species in terms of susceptibility to the tested substances, and encourage to continue research on the resistance of Fusarium spp. to various fungicidal agents.     

Calcium signaling and copper toxicity in <Emphasis Type="Italic">Saccharomyces cerevisiae</Emphasis> cells

To respond to metal surpluses, cells have developed intricate ways of defense against the excessive metallic ions. To understand the ways in which cells sense the presence of toxic concentration in the environment, the role of Ca²⁺ in mediating the cell response to high Cu²⁺ was investigated in Saccharomyces cerevisiae cells. It was found that the cell exposure to high Cu²⁺ was accompanied by elevations in cytosolic Ca²⁺ with patterns that were influenced not only by Cu²⁺ concentration but also by the oxidative state of the cell. When Ca²⁺ channel deletion mutants were used, it was revealed that the main contributor to the cytosolic Ca²⁺ pool under Cu²⁺ stress was the vacuolar Ca²⁺ channel, Yvc1, also activated by the Cch1-mediated Ca²⁺ influx. Using yeast mutants defective in the Cu²⁺ transport across the plasma membrane, it was found that the Cu²⁺-dependent Ca²⁺ elevation could correlate not only with the accumulated metal, but also with the overall oxidative status. Moreover, it was revealed that Cu²⁺ and H₂O₂ acted in synergy to induce Ca²⁺-mediated responses to external stress.     

木粉/壳聚糖接枝丙烯酸-丙烯酰胺吸附树脂对二元重金属离子溶液中Pb2+的吸附

采用自制木粉/壳聚糖接枝丙烯酸-丙烯酰胺吸附树脂R1、R2、R3对二元金属离子Cu2 +/pb2和Zn2+/pb2+溶液中的吸附性能进行了较系统考察.pb2+离子溶液中存在竞争离子Cu2+、Zn2+时,随竞争离子浓度增加,3种吸附树脂R1、R2、R3对pb2+的吸附量明显下降,而竞争离子吸附量显著增加.二元溶液中各金属离子浓度相同时,3种树脂对竞争离子Cu2+、Zn2+的吸附量大于对pb2+的吸附量;各溶液中分别加入NaCl及NaNO3、尿素后,对pb2+离子的吸附量下降迅速.随吸附树脂用量增加,竞争离子Cu2+、Zn2+的吸附量逐渐减小,pb2+的吸附量在吸附树脂用量0.10 g/L(Zn2 +/pb2+溶液)或0.15 g/L(Cu2+/pb2+溶液)时出现最大值.溶液pH值对树脂吸附性能有显著影响.3.0＜pH＜5.O时,3种树脂对竞争离子和pb2+的吸附量快速增大;5＜ pH ＜9时,树脂对竞争离子和pb2+的吸附量基本不变;9＜pH＜ll时,树脂对pb2+的吸附量减小,而对竞争离子的吸附量或增大或减小.     

电极-SBBR处理含铜有机污水

采用电极一SBBR系统去除Cu^2＋,考察了电流强度,IA竞争离子（阴离子SO4^2-、NO3^-、CL^-和阳离子Zn^2＋、Ph^2＋）、初始含Cu^2＋量及溶液pH值对除铜效除果的影响。结果表明,当电流强度为40mA时Cu^2＋去除率最高为98％。投加阴（SO4^2-、NO3^-、Cl^-）、阳（Zn^2＋、Pb^2＋）离子均会引起出水Cu^2＋浓度的增加,且Cl^-和Ph^2＋含量分别为45mg／L和30mg／L时对Cu^2＋去除的影响更为显著。进水Cu^2＋浓度为30mg／L时,Cu^2＋去除率最高为98．48％,当进水Cu^2＋≥70mg／L时,出水Cu^2＋浓度不能达标。酸性（pH4．0～4．5）与碱性（pH9．0～10．0）条件均不利于Cu^2＋的去除,且酸性条件的负面影响更显著．当pH为4．5～7．5时．Cu^2＋去除率最高为97．78％。     

改性荞麦壳对水溶液中Cu~(2+)离子吸附效果及机理

以柠檬酸对荞麦壳进行化学改性,改性后荞麦壳吸附剂对Cu2+的吸附量增加。研究了不同pH、吸附剂投入量、浓度和时间对吸附效果的影响。在pH值为5.5,Cu2+初始浓度50 mg/L,吸附剂投入量为1 g,吸附时间为120 min的条件下,Cu2+的吸附量达到较大值。通过用改性荞麦壳吸附剂对Cu2+的热力学吸附过程的分析,结果表明,改性荞麦壳吸附剂符合Langmuir吸附等温模式,改性荞麦壳吸附剂对Cu2+的吸附存在化学吸附,改性荞麦壳的最大吸附量可以达2.26 mg/g。研究改性荞麦壳吸附剂吸附Cu2+的动力学特性,吸附动力学行为可用准二级速率方程进行很好的描述,准二级吸附速率常数随温度升高而增大。准一级速率方程和颗粒扩散模型可以较好地描述吸附初始阶段,Cu2+浓度较高,颗粒内扩散;吸附后期,Cu2+浓度较低,受到颗粒外扩散的控制。总之,整个吸附过程可能是多种动力学机理共同作用的结果。     

Cu2+、Zn2+对生物脱氮系统的影响

Cu²⁺和Zn²⁺是污水处理工艺中经常遇到的金属离子。在驯化好的活性污泥系统中,研究了金属离子Cu²⁺和Zn²⁺在0～100 mg/L浓度下对活性污泥生物脱氮系统的影响。试验发现Cu²⁺＞5 mg/L、Zn²⁺＞30 mg/L时,对硝化过程具有明显的抑制作用,在同样浓度的试验条件下Cu²⁺对硝化过程的抑制作用比Zn²⁺大。Cu²⁺≤0.5 mg/L时对反硝化过程具有一定的促进作用,有助于提高TN的去除效果;Cu²⁺＞0.5 mg/L时,对反硝化产生抑制作用,随着浓度的增加,TN去除率逐渐下降。Zn²⁺不影响反硝化过程,仅在大于30 mg/L时,对硝化过程产生抑制作用。重金属Cu²⁺对生物脱氮系统的影响明显强于Zn²⁺。     

Chromate reduction on humic acid derived from a peat soil--exploration of the activated sites on HAs for chromate removal

Humic substances are a major component of soil organic matter that influence the behavior and fate of heavy metals such as Cr(VI), a toxic and carcinogenic element. In the study, a repetitive extraction technique was used to fractionate humic acids (HAs) from a peat soil into three fractions (denoted as F1, F2, and F3), and the relative importance of O-containing aromatic and aliphatic domains in humic substances for scavenging Cr(VI) was addressed at pH 1. Spectroscopic analyses indicated that the concentrations of aromatic C and O-containing functional groups decreased with a progressive extraction as follows: F1>F2>F3. Cr(VI) removal by HA proceeded slowly, but it was enhanced when light was applied due to the production of efficient reductants, such as superoxide radical and H(2)O(2), for Cr(VI). Higher aromatic- and O-containing F1 fraction exhibited a greater efficiency for Cr(VI) reduction (with a removal rate of ca. 2.89 mmol g(-1) HA under illumination for 3 h). (13)C NMR and FTIR spectra further demonstrated that the carboxyl groups were primarily responsible for Cr(VI) reduction. This study implied the mobility and fate of Cr(VI) would be greatly inhibited in the environments containing such organic groups.     

新型重金属捕集剂NBMIPA处理含铜汞废水

研究了以间苯二甲酰氯和巯基乙胺盐酸盐为原料合成的重金属捕集剂NBMIPA对单一Cu2＋、Hg2＋电镀废水的捕集性能。结果研究表明,NBMIPA对Cu2＋和Hg2＋的捕集性能优良,NBMIPA投加量越大,捕集性能越高;NBMIPA对pH具有较宽适应性。NBMIPA对于单一含铜废水可无需调pH,投加捕集剂量为废水中含量的4～5倍（摩尔比）,静置后其上层清夜中所含Cu2＋为0.38 mg/L,Cu2＋的去除率可达99.5%以上;当NBMIPA的投加量（摩尔比）是Hg2＋的3.5～4.5倍时,Hg2＋的去除率达到99.83%,残余Hg2＋浓度为0.032 mg/L。     

The spectroscopic studies of humic acid extracted from sediment collected at different seasons

Gocza?kowice Reservoir is the biggest water reservoir in the south of Poland. For our studies bottom sediments were collected from eight different places of the reservoir at various seasons of the year.EPR spectroscopy was applied to analyse both quantitatively and qualitatively the humic acids (HA) present in the samples. EPR spectra of the extracted HA exhibited broad lines from the paramagnetic metal ions and narrow lines from free radicals. The values of the free radical concentration obtained for HA amounted to 1.14-13.6 × 1016 spin g⁻¹ depending on the season and the place of sample collection. The values of the g factor obtained for HA were of the range 2.0027-2.0035.The EPR studies show that HA extracted from bottom sediment collected at various points of the Gocza?kowice Reservoir exhibit similar physical-chemical properties. It was also observed that the depth of the reservoir affects the content of the oxygen functional groups as well as the free radical concentration in HA.The identification of the functional groups was done by means of IR. UV/VIS spectroscopy was used to estimate the maturity of the HA.