Distribution of heavy metals in a sewage oxidation pond and their adsorption in residual solid (sewage sludge ash)

Abstract

Electrometric studies were carried out on the interaction of heavy metal ions such as manganese, chromium, nickel, copper, zinc, cadmium and lead with the extracted organic matter, humic and fulvic acid from the sludge in a sewage oxidation pond. The distribution of heavy metals was between 60 and 97%, which is associated with the solid waste (sludge) of the oxidation pond. The adsorption/removal efficiency of metal ions onto the sludge ash was more than 90% and 97%, respectively, in the pure system. To obtain the ash, the sludge was burnt at 500°C, treated with nitric acid (1+1) to leach out all the metals and then filtered; the residue left on the filter paper was the pure ash. Both this and that coated with organic matter were studied. The adsorption isotherm for metals, humic/fulvic acids and metal-humic/fulvic acid complexes in the metal-free sludge ash and in the organic matter in the pure system were studied using the Freundlich relationship. Good agreement was found suggesting that sediment and humic/fulvic acids have an important role in the mobility, dispersion and sedimentation of metal ions in an aquatic environment. More of these heavy metals are removed in the pure system than in the natural system. This may be due to the lesser availability of humic and fulvic acids in the lagoons during the short detention time of sewage in suspension in the oxidation pond, whereas the sludge which has settled to the bottom of the pond for several years contains rich decomposed organic matter in the form of humic and fulvic acids containing heavy metals. Such pure systems could be useful for the effective removal of heavy metals.     

Impact of application of organic waste materials on microbial and enzyme activities of mine soils in the Lusatian coal mining region

The objective of the present work was to study the short-term stimulation of microbial and enzyme activity in mine soils by application of organic waste materials in lysimeter and mesocosm studies. The mine soils derived from tertiary and quaternary deposits were ameliorated with brown coal filter ash (tertiary deposits) and lime (quaternary deposits). At the beginning of recultivation the soils were treated with varying amounts of sewage sludge, coal sludge, composted sewage sludge and compost to a depth of 30 cm. In the first 2 years after application of organic waste materials we found a very low level of microbial properties especially in the sandy materials from quaternary deposits but a significant increase in microbial respiration, substrate induced respiration and enzyme activities like invertase and alkaline phosphatase with increasing application rates of sewage sludge, compost and sewage sludge mixed with coal sludge. This can be explained by an increase in organic matter and nutrient content of the soils and an improvement of soil physical properties such as water and nutrient retention capacity. Additionally it can be assumed, that constituents of the coal admixtures of tertiary deposits can be mineralised or converted by the soil microorganisms. In the tertiary materials ameliorated with brown coal ash the highest amounts of microbial and enzyme activities were measured after application of nitrogen-rich sewage sludge or very high amounts of mature compost mainly consisting of green waste. Compared with sewage sludge the stimulating effects of composted sewage sludge were quite lower because of organic matter fragmentation and a reduced energy and nutrient supply to soil microorganisms. This revised version was published online in June 2006 with corrections to the Cover Date.     

Cadmium(II) sorption from water samples by powdered marble wastes

Abstract

A series of batch adsorption experiments were carried out, with the aim of removing cadmium ions from aqueous solutions and water samples using powdered marble wastes (PMW) as an effective inorganic sorbent. PMW is inexpensive, widespread, and may be considered as environmental problem. The main parameters (i.e. solution pH, sorbent and cadmium concentrations, stirring time, and temperature) influencing the sorption process were investigated. The results obtained for sorption of cadmium ions onto PMW are well described by the Freundlich and Langmuir models. The Dubinin-Radushkevick (D–R) isotherm model was applied to describe the nature of the adsorption of the metal ion; it was found that the adsorption process was chemical in nature. The thermodynamic parameters were also calculated from the Gibbs free energy change (ΔG°), enthalpy (AH°) and entropy (ΔS°). These parameters indicated that the adsorption process of cadmium(II) ions on PMW was spontaneous and endothermic in nature. Under the optimum experimental conditions employed the removal of ca ~100% of Cd²⁺ ions was attained. The procedure was successfully applied to removal of the cadmium ions from aqueous and various natural water samples. The adsorption mechanism is discussed.     

Adsorption of heavy metals onto sewage sludge-derived materials

Two materials were produced from sewage sludge by: (1) pyrolysis of dried sewage sludge (PS); (2) chemical activation of dried sewage sludge with ZnCl(2) followed by pyrolysis (AS). The aim was to study the application of these materials for metal purification from water and to determine the efficiency of each material. Although AS displayed higher capacity, both PS and AS were able to adsorb these metals and the preferential order was equal: Hg(II)>Pb(II)>Cu(II)>Cr(III). For each metal-adsorbent pair, metal adsorption was highly pH dependent. In all cases the equilibrium was well described both by the Langmuir and the Freundlich isotherms. At the corresponding optimum pH, AS showed the following adsorption capacities: 175.4, 64.1, 30.7 and 15.4 mg/g of Hg(II), Pb(II), Cu(II) and Cr(III), respectively. These results indicate the potential application of these sewage sludge based adsorbents for the treatment of metal polluted effluents.     

Reuse of waste materials as growing media for ornamental plants

The use of different waste materials: pine bark, coconut fibre and sewage sludge as substrates in the production of ornamental plants was studied, with an special interest on the suitability of coconut fibre as growing substrate for conifer plants. The plant species tested were Pinus pinea, Cupressus arizonica and C. sempervirens and the substrate mixtures were: (1) pine bark, (2) pine bark with 15% of sewage sludge compost, (3) pine bark with 30% of sewage sludge compost, (4) coconut fibre, (5) coconut fibre with 15% of sewage sludge compost and (6) coconut fibre with 30% of sewage sludge compost. Substrates were physically and chemically well characterized, and 75-cm plants were grown on them for one year. Plant and substrate status were periodically tested along the experiment. As biosolid recycling is the main objective of the present work, the mixtures with 30% of composted sewage sludge will be the most convenient substrate to use. For C. sempervirens and C. arizonica, a mixture between pine bark or coconut fibre and 30% of biosolid compost in volume gave the best results, but the lower cost of the pine bark than the coconut fibre substrate indicated the use of the PB+30% CSS. For P. pinea the research of new combinations between waste products is recommended to attain better results.     

Use of composted sewage sludge in growth media for broccoli

In this study, the use of composted sewage sludge (CSS) as a binary component with peat (P) in growth media for a horticultural crop, broccoli (Brassica oleracea var. Botryti cv. Marathon), was evaluated. Four treatments were established, based on the addition of increasing quantities of composted sewage sludge to peat (0%, 15%, 30% and 50%, v/v). Physical, physico-chemical and chemical analyses of the different mixtures of CSS and P were made. Plant growth, biomass production and macronutrient (N, P, K, Ca, Mg), micronutrient (Fe, Cu, Mn, Zn) and heavy metal (Pb, Ni, Cd, Cr) contents of plants were determined. The addition of CSS to P increased plant nutrient and heavy metal contents of plants and electrical conductivity (EC) and bulk density values of the substrates. The use of CSS did not affect the germination rate, even at 50% compost. For broccoli growth, the highest yield was obtained with the medium prepared by mixing the peat with 30% of compost; however, the mixture with the most sewage sludge compost (50%) had the greatest contents of macro and micronutrients.     

Application of dried sewage sludge as phenol biosorbent

The aim of this work was to determine the potential application of dried sewage sludge as a biosorbent for removing phenol from aqueous solution. Results showed that biosorption capacity was strongly influenced by the pH of the aqueous solution with an observed maximum phenol removal at pH around 6-8. Biosorption capacity increased when initial phenol concentration was increased to 110 mg/L but beyond this concentration, biosorption capacity decreased suggesting an inhibitory effect of phenol on biomass activity. Biosorption capacity decreased from 94 to 5 mg/g when biosorbent concentration was increased from 0.5 to 10 g/L suggesting a possible competitive effect of leachable heavy metals from the sludge. The effect of Cu2+ on biosorption capacity was also observed and the results confirmed that the phenol biosorption capacity decreased when concentration of Cu2+ in the sorption medium was increased up to 15 mg/L. Desorption of phenol using distilled deionized water was less than 2% suggesting a strong biosorption by the biomass.     

Cunninghamella echinulata a new biosorbent of metal ions from polluted water in Egypt

Thirty-two fungal species were isolated from a polluted watercourse near the Talkha fertilizer plant, Mansoura Province, Egypt. Aspergillus niger, A. flavus, Cunninghamella echinulata and Trichoderma koningii were isolated frequently. On the basis of its frequency, Cunninghamella echinulata was chosen for biosorption studies. Free and immobilized biomass of C. echinulata sequestered ions in this decreasing sequence is: Pb >Cu >Zn. The effects of biomass concentration, pH and time of contact were investigated. The level of ion uptake rose with increasing biomass. The maximum uptake for lead (45 mg/g), copper (20 mg/g) and zinc (18.8 mg/g) occurred at 200 mg/L biomass. The uptake rose with increasing pH up to 4 in the case of Pb and 5 in the case of Cu and Zn. Maximum uptake for all metals was achieved after 15 min. Ion uptake followed the Langmuir adsorption model, permitting the calculation of maximum uptake and affinity coefficients. Treatment of C. echinulata biomass with NaOH improved biosorbent capacity, as did immobilization with alginate. Immobilized biomass could be regenerated readily by treatment with dilute HCl. The biomass-alginate complex efficiently removed Pb, Zn and Cu from polluted water samples. Therefore,Cunninghamella echinulata could be employed either in free or immobilized form as a biosorbent of metal ions in waste water.     

Biosorption of Chromium,Copper, and Nickel Ions by Tamarindus Indica Fruit Nut Testa

Biosorption of chromium, copper, and nickel from aqueous solution by Tamarindus indica fruit nut testa (TFNT) in its pristine and acid-treated forms was studied under equilibrium and column-flow conditions. TFNT, a tannin-containing material, was characterized by energy dispersion x-ray fluorescence (EDXRF) and Fourier transform infrared (FTIR) spectral techniques and surface analysis. The effect of experimental variable parameters such as pH, concentration of metal ions, amount of adsorbent, and contact time on adsorption was investigated. Batch isothermal equilibrium data were analyzed on the basis of Langmuir and Freundlich adsorption isotherms. The kinetics of the adsorption process were studied in terms of Lagergren first-order kinetic model. The monolayer adsorption capacities of pristine and acid-treated forms of tamarind seed coat were found to be 44.8 and 77.5 mg/g for Cr(VI), 55.8 and 99.0 mg/g for Ni(II), and 84.7 and 85.4 mg/g for Cu(II) ions, respectively. The column-flow adsorption data were used to obtain breakthrough curves. The biosorbent loaded with the metal ions was regenerated using 1.0 M HCl and the regenerated bed was used for subsequent adsorption-desorption cycle.     

Biosorption of lead(II), cadmium(II), copper(II) and nickel(II) by anaerobic granular biomass

Biosorption is potentially an attractive technology for treatment of wastewater for retaining heavy metals from dilute solutions. This study investigated the feasibility of anaerobic granules as a novel type of biosorbent, for lead, copper, cadmium, and nickel removal from aqueous solutions. Anaerobic sludge supplied from a wastewater treatment plant in the province of Quebec was used. Anaerobic granules are microbial aggregates with a strong, compact and porous structure and excellent settling ability. After treatment of the biomass with Ca ions, the cation exchange capacity of the biomass was approximately 111 meq/100 g of biomass dry weight which is comparable to the metal binding capacities of commercial ion exchange resins. This work investigated the equilibrium, batch dynamics for the biosorption process. Binding capacity experiments using viable biomass revealed a higher value than those for nonviable biomass. Binding capacity experiments using non-viable biomass treated with Ca revealed a high value of metals uptake. The solution initial pH value affected metal sorption. Over the pH range of 4.0-5.5, pH-related effects were not significant. Meanwhile, at lower pH values the uptake capacity decreased. Time dependency experiments for the metal ions uptake showed that adsorption equilibrium was reached almost 30 min after metal addition. It was found that the q(max) for Pb2+, Cd2+, Cu2+, and Ni2+ ions, were 255, 60, 55, and 26 mg/g respectively (1.23, 0.53, 0.87, and 0.44 mmol/g respectively). The data pertaining to the sorption dependence upon metal ion concentration could be fitted to a Langmiur isotherm model. Based on the results, the anaerobic granules treated with Ca appear to be a promising biosorbent for removal of heavy metals from wastewater due to its optimal uptake of heavy metals, its particulate shape, compact porous structure, excellent settling ability, and its high mechanical strength.     

Removal of Heavy Metals by Waste Tea Leaves from Aqueous Solution

In this paper, tea leaves were shown to be an effective, low‐cost biosorbent. Removal of lead, iron, zinc and nickel from 20 mg/L metal solution by dried biomass of waste tea leaves amounted to 96, 91, 72 and 58 %, respectively, at equilibrium, which followed Langmuir and Freundlich adsorption isotherms. Adsorption of metal was in the order of Pb > Fe > Zn > Ni from 5–100 mg/L of metal solution. From a multi‐metallic mixture, 92.5, 84 and 73.2 % of lead, iron and zinc, respectively, were removed. Fourier transform infrared (FTIR) studies indicated that the carboxyl group was involved in the binding of lead and iron, whereas the amine group was involved in the binding of nickel and zinc. A flow through sorption column packed with dried biomass demonstrated a sorption capacity of 73 mg Pb/g of biomass, indicating its potential in cleaning metal containing wastewater. The metal laden biomass obtained could be disposed off by incineration.     

Characterization of organic matter microstructure dynamics during co-composting of sewage sludge, barks and green waste

A microstructure characterization study using transmission electron microscopy (TEM) was conducted to specify organic matter dynamics during the co-composting process of sewage sludge, green waste and barks. TEM results showed that ligneous and polyphenolic compounds brought by barks were not biodegraded during composting. Green waste brought more or less biodegraded ligneous constituents and also an active microbial potential. Chloroplasts and sludge flocs appeared to be relevant indicators of green waste and sewage sludge in composted products, as they were still viewable at the end of the process. TEM characterization of the final product highlighted two main fractions of organic matter, one easily available and a more recalcitrant one, and also a remaining microbial activity. Thus microstructure characterization appeared to be an appropriate way of taking the heterogeneity of the organic constituents' size and composition into account when attempting to specify such compost quality parameters as maturity and stability.     

Effects of moisture content and initial pH in composting process on heavy metal removal characteristics of grass clipping compost used for stormwater filtration

Heavy metals are common contaminants in stormwater runoff. One of the devices that can be used to effectively and economically remove heavy metals from runoff is a yard waste compost stormwater filter. The primary goal of composting is to reduce waste volume rather than to produce stormwater filter media. Moisture content (MC) and initial pH, the two important parameters in composting, were studied for their effects on yard waste volume reduction and heavy metal adsorption performances of the compost. The main objective of this investigation was to examine whether the conditions that provided high yard waste volume reduction would also result in compost with good heavy metal removal performances. Manila grass was composted at different initial pHs (5–9) and MCs (30–70%) and the composts were used to adsorb cadmium, copper, lead and zinc from water. Results indicated that MC is more critical than initial pH for both volume reduction and production of compost with high metal adsorption performances. The most optimal conditions for the two attributes were not exactly the same but lower MCs of 30–40% and pH 7 or higher tended to satisfy both high volume reduction and effective metal adsorption.     

Fixed-bed biosorption of Cu2+ by polyacrylonitrile-immobilized dead cells of Saccharomyces cerevisiae

Dead cells of Saccharomyces cerevisiae 54 were immobilized by entrappment in polyacrylonitrile. The beads obtained were used to adsorb copper in an up-flow fixed-bed column. The effect of polymer content and cell loading were studied to optimize the porosity and the efficiency in copper removal of the biosorbent beads in a batch system. The optimal concentration of the polyacrylonitrile was assumed to be 12%(w/v) and a concentration of 0.5 g cell dry weight in 1 g polymer was most effective in adsorption of Cu²⁺. The adsorption capacity of this biosorbent was 27 mg Cu²⁺/g dry biomass at 200 mg/l initial concentration of copper ions. Adsorption of Cu²⁺ in a batch system was studied using different initial concentrations of the solute. The optimal conditions in the up-flow column of the following parameters were determined: flow rate, bed height, and initial concentration of Cu²⁺ of the solutions. Results of fixed-bed biosorption showed that breakthrough and saturation time appeared to increase with the bed height, but decrease with the flow rate and the initial concentration. The linearized form of the Thomas equation was used to describe dynamic adsorption of metal ions. As a result, the adsorption capacity of the batch system and the column system was compared. Desorption of copper ions was achieved by washing the column biomass with 0.1 M HCl at an eluent flow rate of 1 ml/min. The reusability of the immobilized biomass was tested in five consecutive adsorption-desorption cycles. The regenerated beads retained over 45% of their original adsorption capacity after five A/D cycles. This revised version was published online in August 2006 with corrections to the Cover Date.     

Differences on nitrogen availability in a soil amended with fresh, composted and thermally-dried sewage sludge

Anaerobically-digested sludge called fresh sludge (F), composted sludge (C) and thermally-drying sludge (T), all from the same batch, were applied to the surface of a calcareous Udic Calciustept with loamy texture. Dosage equivalent was 10 t ha(-1) of dry matter. The concentration of mineral nitrogen (ammonium and nitrate) in the soil was measured in order to estimate the effects of the post-treatments to which the different kinds of sewage sludge are subjected in relation to the availability of N in the surface layer of the soil. The most significant differences in NH(4)-N and NO(3)-N concentrations due to the transformation of the organic matter were observed during the first three weeks following soil amendment. Thermally-dried and composted sludge initially displayed higher concentrations of ammonium and nitrate in soil. Five months after the amendment, soil applied with fresh sludge showed the highest concentrations of NH(4)-N and NO(3)-N (6.1 and 36.6 mg kg(-1), respectively). It is clear that the processes of composting and thermal-drying influence the bioavailability of nitrogen from the different types of sewage sludge.     

Effectiveness of Biosorption-Assisted Microfiltration Process for Treatment of Domestic Wastewater

The efficiency of a biosorbent prepared from Eichhornia crassipes roots (ECR) was explored for the treatment of domestic sewage water in combination with low-cost ceramic microfiltration membrane. Batch sorption studies were conducted as a function of biosorbent dose, initial chemical oxygen demand (COD) loading, and temperature. Sorption equilibrium data of varying initial COD values (116–800 mg/L) indicated high potential of ECR for COD removal. Using 0.25 g/L of biosorbent dose, the equilibrium adsorption capacity was obtained as 2480 mg/g at 20°C for an initial COD loading of 800 mg/L. Microfiltration study was performed using ceramic membrane made from composition of α-alumina and clay. The effect of operating parameters on filtration characteristics was observed in terms of permeate flux. Permeate samples were characterized in terms of various parameters both for the direct filtration, as well as biosorbent-assisted filtration. The filtration behavior of wastewater at varying transmembrane pressure was explained using various membrane fouling models. The results suggested that microfiltration of domestic wastewater with incorporation of biosorbent (0.25 g/L) was highly effective for removal of organic load (>90%), turbidity (>99%), and total suspended solids (TSS) (93–95%) and the treated water quality was suitable for reuse in various purposes, such as gardening, floor and car washing, etc.     

Spontaneous Cr(VI) and Cd(II) biosorption potential of native pinnae tissue of Pteris vittata L., a tropical invasive pteridophyte

Heavy metal pollution is a prevalent and critical environmental concern. Its rampancy is attributed to indiscriminate anthropogenic activities. Several technologies including biosorption have been continuously researched upon to overcome the limitations of the conventional method of treatments in removal of heavy metals. Biosorption technology involves the application of a biomass in its nonliving form. Pteris vittata L., a pteridophyte, considered as an invasive weed was investigated in the present study as a potential decontaminant of toxic metals, Cr(VI) and Cd(II). The adsorption capacity of the biosorbent for Cr(VI) and Cd(II) under equilibrium conditions was investigated. The morphology, elemental composition, functional groups, and thermal stability of the biosorbent before and after metal loading were evaluated. At 303?K and an equilibrium time of 120?min, the maximum loading of Cr(VI) on the biosorbent was estimated to be 166.7?mg/g at pH 2 and Cd(II) to be 31.3?mg/g at pH 6. Isotherm models, kinetic studies, and thermodynamic studies indicated the mechanisms, chemisorption, ion exchange and intraparticle diffusion, controlling the Cr(VI) and Cd(II) uptake, respectively. The interactive effect of multi-metal ions in binary component systems was synergistic for Cd(II) uptake. The results validate the toxic metal removal potency of the biosorbent.     

Adsorptive removal of copper and nickel ions from water using chitosan coated PVC beads

A new biosorbent was developed by coating chitosan, a naturally and abundantly available biopolymer, on to polyvinyl chloride (PVC) beads. The biosorbent was characterized by FTIR spectra, porosity and surface area analyses. Equilibrium and column flow adsorption characteristics of copper(II) and nickel(II) ions on the biosorbent were studied. The effect of pH, agitation time, concentration of adsorbate and amount of adsorbent on the extent of adsorption was investigated. The experimental data were fitted to Langmuir and Freundlich adsorption isotherms. The data were analyzed on the basis of Lagergren pseudo first order, pseudo-second order and Weber-Morris intraparticle diffusion models. The maximum monolayer adsorption capacity of chitosan coated PVC sorbent as obtained from Langmuir adsorption isotherm was found to be 87.9 mg g(-1) for Cu(II) and 120.5 mg g(-1) for Ni(II) ions, respectively. In addition, breakthrough curves were obtained from column flow experiments. The experimental results demonstrated that chitosan coated PVC beads could be used for the removal of Cu(II) and Ni(II) ions from aqueous medium through adsorption.     

Removal of Pb2+ from aqueous system by live Oscillatoria laete-virens (Crouan and Crouan) Gomont isolated from industrial effluents

Cyanobacteria have been found to be potential biosorbents of metal ions from waste water. The Pb(2+) removal capacity of growing cells of indigenous cyanobacterium Oscillatoria laete-virens (Crouan and Crouan) Gomont was studied under batch experiments and it was found capable of removing Pb(2+) of lower concentrations (below 100?mg L(-1)). The effects of different concentrations of Pb(2+), on the growth rate of alga were also evaluated. The research parameters include the pH of the solution, contact time, initial concentration of Pb(2+), and culture density. Of the parameters studied, the pH of the solution was found to be the most crucial. The removal of Pb(2+) peaked at an initial pH of 5. The data obtained from the equilibrium experiments were found well fitting with the Langmuir isotherm with a maximum sorptive capacity (q (max)) of 20.36?mg?g(-1), indicating a good biosorbtive potential of growing cells. This was confirmed using scanning electron microscope and energy dispersive X-ray analysis, which showed the adsorption of lead on the surface of the cell. The species could tolerate a concentration as high as 60?mg L(-1) of Pb(2+). It was observed that the removal obeyed the pseudo-second-order kinetics. The percentage removal was found to decrease with increasing metal concentration, from 10 to 100?mg L(-1). FTIR analysis indicates the involvement of amino, carboxylic and amide groups in the sorption process. Among the desorbing agents evaluated, an efficient recovery of 90.2?% was achieved by HCl, in 24?h. Thus Oscillatoria laete-virens (Crouan and Crouan) Gomont seems to be a promising metal biosorbent for the treatment of Pb(2+), in waste waters.     

Evaluation of a countercurrent biosorption system for the removal of lead and copper from aqueous solutions

Abstract: An automated bench-scale countercurrent biosorption system (CBS) has been designed for the removal of metals from aqueous effluents. The system has been tested with activated sludge microorganisms as a biosorbent and lead and copper as model metals. Nearly 5 1 of a lead nitrate solution at 100 mg l⁻¹ of lead have been treated down to a final concentration of 0.1 mg l⁻¹ (99.9% removal) by using 4.8 g of dry biosorbent. Under similar conditions, copper chloride solutions at 100 mg 1⁻¹ of copper were treated down to a final concentration of 35–45 mg l^−l representing 60% removal. The advantage of the CBS is to maximize metal concentration in the biosorbent, from which the metal may thereby be recovered if desired. In addition, the CBS minimizes metal concentration in the treated effluent, which is the first objective of the treatment.