Modification of rice hull and sawdust sorptive characteristics for remove heavy metals from synthetic solutions and wastewater

In this work two modified agricultural residues, rice hull and sawdust were examined as sorbents to remove heavy metals Pb(II), Cd(II), Zn(II), Cu(II) and Ni(II) from synthetic solutions or wastewater samples. To modify their sorptive characteristics, samples were treated with HCl, NaOH and heat. The sorption of the heavy metals from the synthetic solutions was increased with pH and initial concentration. In pH 5, Pb(II) and Cd(II) showed the highest sorption and Cu(II), Zn(II) and Ni(II) showed the following orders, respectively. Sorption capacity of rice hull was higher than sawdust. The modifications changed the sorption capacity of the natural sorbents in the following order base>heat>natural>acid. The sorption isotherms of sorbents were best described by the Freundlich and Langmuir models. The basic treated rice hull and sawdust followed by the heat treated rice hull sorbed the maximum of heavy metals from the industrial wastewater samples. In the column experiment, the synthetic solutions and the wastewater samples gave almost the same results as the suspensions. The recovery of the columns using water and HCl showed positive results. Commercial sorbents removed Pb(II), Zn(II) and Ni(II) a little more than rice hull.     

Membrane filtration of chlorination and extraction stage bleach plant effluent in Indian paper Industry

The present study was carried out for the treatment of effluent from the chlorination and extraction stages of a bleach plant at an Indian pulp and paper mill. The effluents were taken from an integrated paper mill employing OCE_OPHH sequence for the bleaching of hardwood pulp. Effluent was treated via ultrafiltration (UF), nanofiltration (NF), and reverse osmosis (RO). Thin film composite spiral-wound modules, having cross flow membranes composed of polysulfone and polyamide, were used in the study. Three initial inlet pressures were used for the UF and NF; 6.8, 10.3, and 13.7 bar. For RO initial inlet pressures of 10.3 bar, 13.7 bar and 17.2 bar, were taken in different trials. The retentate from each experiment was recycled back to the feed and retreated until the inlet pressure increased to the maximum cut-of pressure for each membrane. The UF permeate was fed to the NF, which was subsequently fed to the RO. Variations in the trans-membrane pressure and permeate flux were assessed. The removal of pollutants and fouling indices were obtained for each membrane at each initial inlet pressure.     

Sorption of metal ions on lignite and the derived humic substances

The study presents results of sorption of metal ions (Pb2+, Zn2+, Cu2+, and Cd2+) onto lignite mined in South Moravia, Czech Republic, and solid humic substances (humin and humic acid) derived from it. The efficiency of these sorbents has been studied as a function of contact time, solution pH, and metal concentration. The sorption efficiencies were higher for humin and lower for humic acid samples than for the original lignite. With its high sorption capacities of several mmol/g, particularly for Pb2+ and Cd2+, the South Moravian lignite can provide a cheap source material for preparation of sorbents utilizable in removal of toxic metals from wastewaters.     

Functionalised membranes remove and recover dissolved heavy metals

The use of microfiltration membrane-based sorbents, containing multiple functional group is a novel way of achieving high metal sorption under convective flow conditions. This article looks at research carried out at the University of Kentucky which led to the development of a new class of polyamino acid functionalised membranes that are able to capture dissolved metals from aqueous streams by sorption onto exchange sites which have been chemically attached to membrane pores convectively. The work also shows that a variety of membrane materials — cellulose, silica and cellulose acetate — can be used for heavy metal sorption at capacities as high as 1.9 g/g (5 mg/cm² membrane).     

Effect of EDTA on divalent metal adsorption onto grape stalk and exhausted coffee wastes

In the present work, two industrial vegetable wastes, grape stalk, coming from a wine producer, and exhausted coffee, coming from a soluble coffee manufacturer, have been investigated for the removal of Cu(II) and Ni(II) from aqueous solutions in presence and in absence of the strongly complexing agent EDTA. Effects of pH and metal-EDTA molar ratio, kinetics as a function of sorbent concentration, and sorption equilibrium for both metals onto both sorbents were evaluated in batch experiments. Metal uptake was dependent of pH, reaching a maximum from pH around 5.5. EDTA was found to dramatically reduce metal adsorption, reaching total uptake inhibition for both metals onto both sorbents at equimolar metal:ligand concentrations. Kinetic results were successfully modelled by means of the pseudo second order model. Langmuir and Freundlich models were used to describe the sorption equilibrium data. Grape stalk showed the best performance for Cu(II) and Ni(II) removal in presence and in absence of EDTA, despite exhausted coffee appears as less sensitive to the presence of complexing agent. The performance of Cu(II) and Ni(II) sorption onto grape stalk in a continuous flow process was evaluated. In solutions containing EDTA, an initial metal concentration in the outlet flow corresponding to the complexed metal fraction was observed from the beginning of the process. A high metal recovery yield (>97%) was achieved by feeding the metal-loaded column with 0.05 M HCl.     

Untreated coffee husks as biosorbents for the removal of heavy metals from aqueous solutions

The objective of this work was to propose an alternative use for coffee husks (CH), a coffee processing residue, as untreated sorbents for the removal of heavy metal ions from aqueous solutions. Biosorption studies were conducted in a batch system as a function of contact time, initial metal ion concentration, biosorbent concentration and pH of the solution. A contact time of 72 h assured attainment of equilibrium for Cu(II), Cd(II) and Zn(II). The sorption efficiency after equilibrium was higher for Cu(II) (89-98% adsorption), followed by Cd(II) (65-85%) and Zn(II) (48-79%). Even though equilibrium was not attained in the case of Cr(VI) ions, sorption efficiency ranged from 79 to 86%. Sorption performance improved as metal ions concentrations were lowered. The experimental sorption equilibrium data were fitted by both Langmuir and Freundlich sorption models, with Langmuir providing the best fit (R2>0.95). The biosorption kinetics was determined by fitting first and second-order kinetic models to the experimental data, being better described by the pseudo-second-order model (R2>0.99). The amount of metal ions sorbed increased with the biosorbent concentration in the case of Cu(II) and Cr(VI) and did not present significant variations for the other metal ions. The effect of the initial pH in the biosorption efficiency was verified in the pH range of 4-7, and the results showed that the highest adsorption capacity occurred at distinct pH values for each metal ion. A comparison of the maximum sorption capacity of several untreated biomaterial-based residues showed that coffee husks are suitable candidates for use as biosorbents in the removal of heavy metals from aqueous solutions.     

Selective removal of Pb(II), Cd(II), and Zn(II) ions from waters by an inorganic exchanger Zr(HPO3S)2

The present study reported synthesis of a new inorganic exchanger, i.e., zirconium hydrogen monothiophosphate [Zr(HPO₃S)₂, denoted ZrPS] and its selective sorption toward Pb(II), Cd(II) and Zn(II) ions. ZrPS sorption toward all the three metals is dependent upon solution pH due to the ion-exchange nature. As compared to another inorganic exchanger zirconium phosphate [Zr(HPO₄)₂, denoted ZrP], ZrPS exhibits highly selective sorption toward these toxic metals from the background of calcium ions at great levels. Such sorption preference is mainly attributed to the presence of –SH group in ZrPS, as further demonstrated by FT-IR analysis and XPS study. Moreover, ZrPS particles preloaded with heavy metals could be efficiently regenerated with 6 M HCl for multiple use without any noticeable capacity loss. All the experimental results indicated that ZrPS is a promising sorbent for enhanced heavy metals removal from contaminated water.     

Adsorption behavior of Zn(II) on calcinated Chinese loess

Chinese loess has proven to be effective in removing Zn(II) from aqueous solutions, but the resultant adsorbent-water slurry is difficult to separate. In this paper, the crude loess was calcinated to improve the separation efficiency of slurries in terms of sedimentary rate by increasing the particle sizes of the adsorbent. The sorption capacities of different sorbents, including crude loess, calcinated loess, de-organic crude loess and acid-treated calcinated loess, were obtained and sequenced. The adsorption capacity of the calcinated loess towards Zn(II) was found to be as high as 113.6 mg g(-1). The adsorption isotherms and kinetics of calcinated loess were best-fit with the Freundlich isotherm and the pseudo-second order kinetics, respectively. The thermodynamic analysis revealed that the adsorption was exothermic and spontaneous with a high preference for Zn(II) removal. The adsorption of Zn(II) on calcinated loess implies an ion exchange of the solute with calcite and goethite due to the observed FT-IR and XRD patterns as well as the predicted mean free energies (-11.58 to -9.28 kJ mol(-1) by D-R model). The byproduct of adsorption can be purified and refreshed by using a 0.01 M HCl solution.     

Treatment of refractory organics from membrane rejects using ozonation

The reject water or retentate generated from membrane application for recovery of water from tannery wastewater treatment contains certain refractory organics. These refractory organics are present in substantial quantity in the condensate of reject water also. Hence the treatment of rejects using conventional methods is rather difficult. In this paper, an attempt has been made to treat the reject water from the reverse osmosis (RO) and nano filtration (NF) operation on tannery wastewater using ozonation treatment technique. Ozonation studies on RO and NF rejects indicate that ozone dose of 80 and 100mg/min for 60 and 70 min contact time achieves 59 and 78% chemical oxygen demand (COD) reduction, respectively. The mass balance in ozone indicates the ozone consumption for RO and NF rejects varies from 2.4 to 3.4 and 2.8 to 4.5 g/g of COD removed respectively. The results suggest that ozonation of RO and NF rejects would significantly reduce the refractory organic pollutant loading into the environment from wastewater reuse facility.     

Removal of cyanobacterial metabolites by nanofiltration from two treated waters

Cyanobacterial metabolites, both toxic and non-toxic, are a major problem for the water industry. Nanofiltration (NF) may be an effective treatment option for removing organic micropollutants, such as cyanobacterial metabolites, from drinking water due to its size exclusion properties. A rapid bench scale membrane test (RBSMT) unit was utilised to trial four NF membranes to remove the cyanobacterial metabolites, microcystin, cylindrospermopsin (CYN), 2-methylisoborneol (MIB) and geosmin (GSM) in two treated waters sourced from the Palmer and Myponga water treatment plants. Membrane fouling was observed for both treated waters; however, only minor differences were observed between feed waters of differing natural organic matter (NOM) concentration. Low molecular weight cut-off (MWCO), or 'tight' NF, membranes afforded average removals above 90% for CYN, while removal by higher MWCO, or 'loose' NF membranes was lower. MIB and GSM were removed effectively (above 75%) by tight NF but less effectively by loose NF. Microcystin variants (MCRR, MCYR, MCLR, MCLA) were removed to above 90% by tight NF membranes; however, removal using loose NF membranes depended on the hydrophobicity and charge of the variant. Different NOM concentration in the treated waters had no effect on the removal of cyanobacterial metabolites.     

Treatment of hazardous sorbents generated from the adsorption of heavy metals during incineration

The emission of heavy metals during waste incineration can be effectively reduced through the practice of employing non-toxic sorbents. These sorbents can react with toxic metals at high temperatures and create metal binding between them by various physical and chemical mechanisms. After the adsorption process, the used sorbents, which contain heavy metals, need to be desorbed to reduce their potential environmental hazards or provide reusable sorbents for economical aspect. The sorbent's adsorption efficiency is affected by different operating conditions and waste elemental compositions during incineration, which, in turn, affect their desorption characteristics. However, the effects of operating condition and waste elemental composition on the stability of heavy metals in the sorbents and the desorption efficiencies have been little studied. This study investigates the desorption characteristics of heavy metals (Cr, Pb, Cu, and Cd) from the hazardous sorbents with different extracting reagents (H(2)O, HCl, EDTA, and Na(2)S(2)O(5)). The hazardous sorbents were generated under different adsorption time and various input waste elemental compositions during incineration process.     

Biosorption mechanism of nine different heavy metals onto biomatrix from rice husk

A biomatrix was prepared from rice husk, a lignocellulosic waste from agro-industry, for the removal of several heavy metals as a function of pH and metal concentrations in single and mixed solutions. The biomatrix was characterized using scanning electron microscope and Fourier transform infrared spectroscopy, which indicated the presence of several functional groups for binding metal ions. Different experimental approaches were applied to show mechanistic aspects, especially the role of calcium and magnesium present in the biomatrix in ion exchange mechanism. The ultimate maximum adsorption capacity obtained from the Langmuir isotherm increases in the order (mmol/g): Ni (0.094), Zn (0.124), Cd (0.149), Mn (0.151), Co (0.162), Cu (0.172), Hg (0.18) and Pb (0.28). The sorption of Cr(III) onto biomatrix at pH 2 was 1.0 mmol/g. Speciation of chromium, cadmium and mercury loaded on the biomatrix was determined by X-ray photoelectron spectroscopy. The biomatrix has adsorption capacity comparable or greater to other reported sorbents.     

Modified aluminosilicates as low-cost sorbents of As(III) from anoxic groundwater

The utilization of low-grade clay materials as selective sorbents represents one of the most effective possibilities of As removal from contaminated water reservoirs. The simple pre-treatment of these materials with Fe (Al, Mn) salts can significantly improve their sorption affinity to As oxyanions. The natural kaolin calcined at 550 degrees C (mostly metakaolin) and raw bentonite (mostly montmorillonite) pre-treated with Fe(II), Fe(III), Al(III) and Mn(II) salts were used to remove of As from the model anoxic groundwater with As(III) concentration about 0.5 and 10 mg L(-1). All the pre-treating methods were appropriate for bentonite; the efficiency of As(III) sorption varied from 92 to >99%, by the sorption capacity higher than 4.5 mg g(-1). In the case of metakaolin, Fe(II)- and Mn(II)-treatments proved the high sorption efficiency (>97%), while only <50% of As was removed after Fe(III) and Al(III) pre-treatment. The sorption capacities of treated metakaolin ranged from 0.1 to 2.0 mg g(-1).     

Recycling of agricultural solid waste, coir pith: removal of anions, heavy metals, organics and dyes from water by adsorption onto ZnCl2 activated coir pith carbon

The abundant lignocellulosic agricultural waste, coir pith is used to develop ZnCl(2) activated carbon and applied to the removal of toxic anions, heavy metals, organic compounds and dyes from water. Sorption of inorganic anions such as nitrate, thiocyanate, selenite, chromium(VI), vanadium(V), sulfate, molybdate, phosphate and heavy metals such as nickel(II) and mercury(II) has been studied. Removal of organics such as resorcinol, 4-nitrophenol, catechol, bisphenol A, 2-aminophenol, quinol, O-cresol, phenol and 2-chlorophenol has also been investigated. Uptake of acidic dyes such as acid brilliant blue, acid violet, basic dyes such as methylene blue, rhodamine B, direct dyes such as direct red 12B, congo red and reactive dyes such as procion red, procion orange were also examined to assess the possible use of the adsorbent for the treatment of contaminated ground water. Favorable conditions for maximum removal of all adsorbates at the adsorbate concentration of 20 mg/L were used. Results show that ZnCl(2) activated coir pith carbon is effective for the removal of toxic pollutants from water.     

Colloid stable sorbents for cesium removal: preparation and application of latex particles functionalized with transition metals ferrocyanides

In this paper we suggest a principally new approach to preparation of colloid stable selective sorbents for cesium uptake using immobilization of transition metals (cobalt, nickel, and copper) ferrocyanides in nanosized carboxylic latex emulsions. The effects of ferrocyanide composition, pH, and media salinity on the sorption properties of the colloid stable sorbents toward cesium ions were studied in solutions containing up to 200 g/L of sodium nitrate or potassium chloride. The sorption capacities of the colloid sorbents based on mixed potassium/transition metals ferrocyanides were in the range 1.3-1.5 mol Cs/mol ferrocyanide with the highest value found for the copper ferrocyanide. It was shown that the obtained colloid-stable sorbents were capable to penetrate through bulk materials without filtration that made them applicable for decontamination of solids, e.g. soils, zeolites, spent ion-exchange resins contaminated with cesium radionuclides. After decontamination of liquid or solid radioactive wastes the colloid-stable sorbents can be easily separated from solutions by precipitation with cationic flocculants providing localization of radionuclides in a small volume of the precipitates formed.     

New high capacity getter for vacuum insulated mobile LH2 storage tank systems

Current “Non-evaporable getters” (NEGs) are important for the improvement of vacuum by the help of metallic surface sorption of residual gas molecules. High porosity alloys or powder mixtures of Zr, Ti, Al, V, Fe and other metals are the base material for this kind of gas sorbents. The development of vacuum technologies creates new challenges for the field of getter materials. The main sorption parameters of the current NEGs, namely, pumping speed and sorption capacity, have reached certain level limits. Chemically active metals are the basis of NEGs of a new generation. The appearance of new materials with high sorption capacity at room temperature is a long-felt need. It is obvious, that chemically active metals and alloys with reactivity higher, than that of transition metals, can become this kind of materials. The potential of active metals as the strongest gas sorbents is very high. The improved getter materials allow faster pumping speed. The sticking rate on the chemically active surface is significantly higher, and sorption capacity can be increased by up to 104 times (during the life-time of a device the entire getter material reacts with residual gases). The main structural form of the new getter concepts are spherical powders, granules and porous multi-layers. The full pumping performance takes already place at room temperature and the activation temperature can be adjusted between room temperature and 660 °C. The successful insertion of this new chemical getter pump in a mobile double-walled LH₂ tank system shows the very high sorption capacity of all relevant residual gases including H₂. This new invention opens the possibility for significant vacuum improvements especially in the field of H₂ pumping, which is an important challenge in many different vacuum devices and processes.     

Effect of quaternary ammonium cation loading and pH on heavy metal sorption to Ca bentonite and two organobentonites

Sorption of four heavy metals (Pb, Cd, Zn and Hg) to calcium bentonite (Ca bentonite), hexadecyltrimethylammonium bentonite (HDTMA bentonite) and benzyltriethylammonium bentonite (BTEA bentonite) was measured as a function of the quaternary ammonium cation (QAC) loading at 25, 50 and 100% of the clay's cation-exchange capacity (CEC). The effects of pH on the surface charge of the clays and heavy metal sorption were also measured. Sorption of Cd, Pb, and Zn was non-linear and sorption of all three metals by HDTMA and BTEA bentonites decreased as the QAC loading increased from 25 to 100%. In most cases, sorption of these metals to 25% BTEA and 25% HDTMA bentonite was similar to or greater than sorption to Ca bentonite. Hg sorption was linear for both HDTMA and BTEA bentonite. No significant effect on Hg sorption was observed with increasing QAC loading on BTEA bentonite. However, an increase of Hg sorption was detected with increasing QAC loading on HDTMA bentonite. This behavior suggests that a process different than cation exchange was the predominant Hg sorption mechanism. Cd, Pb, and Zn sorption decreased with pH. However, this effect was stronger for Cd and Pb than Zn. Hg sorption varied inversely with pH. QAC loading affected the surface charge of the clays. Twenty-five and 50% loading of BTEA cations increased the negative charge on the clay's surface relative to the untreated clay, without affecting the zero point of charge (ZPC) of the clay. Increased QAC loading on HDTMA bentonite causes the surface charge to become more positive and the ZPC increased. One hundred percent of HDTMA bentonite maintained a positive surface charge over the range of pH values tested. The organoclays studied have considerable capacity for heavy metal sorption. Given that prior studies have demonstrated the strong sorption capacity of organoclays for nonionic organic pollutants, it is likely that organoclays can be useful sorbents for the treatment of effluent streams containing both organic contaminants and heavy metals.     

Metal ion biosorption on chitosan for the synthesis of advanced materials

Chitosan is an aminopolysaccharide that binds metal ions through different mechanisms such as ion exchange, chelation or formation of ternary complex. The sorption performance depends on the characteristics of the solution (pH, presence of ligands, metal speciation) and the properties of the biopolymer (crystallinity, degree of deacetylation, molecular weight). Sorption performance is also controlled by the accessibility and availability of reactive groups (diffusion properties). These interactions chitosan/metal ions can be used for environmental applications (recovery of toxic or valuable metals) but also for the synthesis of new materials. Hybrid materials (chitosan/metal ion composites) can thus be used for manufacturing new sorbents with improved functionalities, supported catalysts, antimicrobial supports and sensors. The physical versatility of the biopolymer is an important criterion for designing these new materials: The conditioning of the material under the form of hydrogel beads, membranes, fibers and hollow fibers, foams and sponges enhances sorption performance and allows developing new applications.     

Sorption of Cd(II) and Se(IV) from aqueous solution using modified rice husk

A carbonaceous sorbent was prepared from rice husk via sulfuric acid treatment. Removal of Cd(II) and Se(IV) from aqueous solution was studied varying time, pH, metal concentration, temperature and sorbent status (wet and dry). Cd(II) sorption was found fast reaching equilibrium within approximately 2 h while Se(IV) sorption was slow reaching equilibrium within approximately 200 h with better performance for the wet sorbent than for the dry. Kinetics data for both metals were found to follow pseudo-second order model. Cd(II) sorption was low at low pH values and increased with pH increase, however, Se(IV) sorption was high at low pH values, and decreased with the rise in initial pH until pH 7. A fall in the final pH was noticed with Cd(II) sorption due to the release of protons indicating an ion exchange mechanism. However, for Se(IV) sorption, a rise in the final pH was observed due to protons consumption in the process. For both metals, sorption fit well the Langmuir equation with higher uptake by rising the temperature. Analysis by scanning electron microscope and X-ray powder diffraction for the sorbent after the reaction with acidified Se(IV) confirmed the availability of elemental selenium, Se(0), as particles on the sorbent surface. The reduction process of acidified Se(IV) to Se(0) is accompanied by surface oxidation. Physicochemical tests showed an increase in sorbent acidity, cation exchange capacity and surface functionality after the reaction with acidified Se(IV) indicating that oxidation processes took place on the sorbent surface. On the other hand, no changes in physicochemical tests were found after Cd(II) sorption indicating the absence of redox processes between Cd(II) and the sorbent.     

城市饮用水膜处理技术

综述了城市饮用水膜处理技术,介绍了新型膜处理技术具有适应的水质范围广,出水水质好,占地面积小等优点,及其在国外的推广应用。这种新型的膜处理技术不仅能有效地去除水中的浊度、 病原微生物和病原寄生虫,纳滤膜还能有效地去除水中的有机污染物,包括常规工艺很难去除的农药等。