Compost produced from organic fraction of municipal solid waste, primary stabilized sewage sludge and natural zeolite

The aim of this work is to present the physicochemical characteristics of the compost produced from dewatered anaerobically stabilized primary sewage sludge (DASPSS), organic fraction of municipal solid waste (OFMSW) and the metal uptaken by zeolite (clinoptilolite). The final results indicated that the composted material produced from clinoptilolite 20% w/w and 80% w/w DASPSS and OFMSW (60% and 40%, respectively) provided better soil conditioning compared to the compost produced from DASPSS. The co-composting products had a higher concentration of total humic and organic matter (O.M.) than the sewage sludge compost. Also, the heavy metals concentration in the final products was in lower concentration than in the sewage sludge compost. The zeolite appeared to uptake a significant (p<0.05) amount of metals. Specifically, the use of 20-25% w/w of clinoptilolite appears to uptake 100% of Cd, 10-15% of Cr, 28-45% of Cu, 41-47% of Fe, Mn 9-24% of Mn, 50-55% of Ni and Pb, and 40-46% of Zn. Although by the application of the composting process, the reduction in dry mass is between 30% and 40% for all samples.     

Influence of clinoptilolite rock on chemical speciation of selected heavy metals in sewage sludge

The chemical speciation of Cd, Cu, Pb, Cr and Ni in Torun municipal sewage sludge is investigated with addition of a natural sorbent (clinoptilolite rock). The total contents of the heavy metals in the sludge are substantially lower than the corresponding limits established by European or Polish legislation excepting nickel only. But the metals concentrations excepting lead exceed significantly the natural background (average contents in soils and in the Earth's crust) in dozens. Application of the sequential chemical extraction indicated that the metals in the sewage sludge are bound mainly (over 50%) in the residual fraction. The metals form the following order by parts of the mobile form: Ni> Cd> Cr> Cu> Pb. Addition of the clinoptilolite to the sludge leads to the metals contents fall in all four fractions of the sequential procedure. Concentrations of mobile forms of cadmium, chromium, copper and nickel decrease by 87, 64, 35 and 24%, respectively, as a result of addition of 9.09% of the clinoptilolite. The total decreases of the metals amount after 9.09% clinoptilolite addition to the sludge are around 11, 15, 25, 41 and 51% for copper, nickel, chromium, cadmium and lead, respectively.     

Total concentrations and speciation of heavy metals in municipal sludge from Changsha, Zhuzhou and Xiangtan in middle-south region of China

The presence of heavy metals in municipal sludge restricts its use for agricultural purposes. In this paper, the bioavailability and eco-toxicity of heavy metals in municipal sludge was evaluated, taking into consideration both the speciation of metals and the local environmental characteristics. The dewatered municipal sludge samples were collected from five sewage plants in Changsha, Zhuzhou and Xiangtan respectively, which are representative cities with characteristics of the middle-south region of China. Some agricultural significant parameters and total metal concentrations in the sludge were determined and the metal speciation was studied by using BCR sequential extraction procedure. It was found experimentally that in general the municipal sludge collected from the five sewage plants was rich in organics, N and P. Except that the sludge from Xia Wan Sewage Treatment Plant showed higher concentrations of heavy metals, the sludge from other plants all showed a low total content of heavy metals with only Cd slightly exceeding the permitted values of the national application standard of acid soil in China (GB18918-2002). The sequential extraction results showed that Cu and Zn were principally distributed in the oxidizable fraction, which meant a high potential toxicity, but the bioavailability of Zn might be overestimated to the soil of Hunan. Pb was mainly in the residual fraction. The distribution of Cd showed no obvious characteristics.     

Impact of thermal treatment on metal in sewage sludge from the Psittalias wastewater treatment plant, Athens, Greece

This paper describes a laboratory study that examined the effect of thermal treatment at four different temperatures on the behavior of heavy metals in the anaerobically treated primary sludge from the Psittalias wastewater treatment plant. The sewage sludge was found to contain significant amounts of heavy metals (Cr, Cu, Fe, Ni, Pb and Zn). The metal form distribution in the sludge samples which was determining by the application of a sequential extraction procedure revealed that a significant portion of metals was embodied in the organic and reducible fractions. Treatment at 105, 250, 650 and 900 degrees C demonstrated significant conversions of the metals to a less mobile form as well as removal by vaporization. By applying sequential analysis, it was found that most of the metals were removed from the initial mobile phases to more stable ones. Also, significant amounts were transformed to the gaseous phase.     

Factorial experimental design for recovering heavy metals from sludge with ion-exchange resin

Wastewaters containing heavy metals are usually treated by chemical precipitation method in Taiwan. This method can remove heavy metals form wastewaters efficiently, but the resultant heavy metal sludge is classified as hazardous solid waste and becomes another environmental problem. If we can remove heavy metals from sludge, it becomes non-hazardous waste and the treatment cost can be greatly reduced. This study aims at using ion-exchange resin to remove heavy metals such as copper, zinc, cadmium, and chromium from sludge generated by a PCB manufacturing plant. Factorial experimental design methodology was used to study the heavy metal removal efficiency. The total metal concentrations in the sludge, resin, and solution phases were measured respectively after 30 min reaction with varying leaching agents (citric acid and nitric acid); ion-exchange resins (Amberlite IRC-718 and IR-120), and temperatures (50 and 70 degrees C). The experimental results and statistical analysis show that a stronger leaching acid and a higher temperature both favor lower heavy metal residues in the sludge. Two-factors and even three-factor interaction effects on the heavy metal sorption in the resin phase are not negligible. The ion-exchange resin plays an important role in the sludge extraction or metal recovery. Empirical regression models were also obtained and used to predict the heavy metal profiles with satisfactory results.     

Total concentrations and fractions of Cd, Cr, Pb, Cu, Ni and Zn in sewage sludge from municipal and industrial wastewater treatment plants

Heavy metals are one of the important factors that affect the final disposal of sewage sludge. In this paper, the metal mobility and bioavailability of heavy metals in sewage sludge were studied by using Community Bureau of Reference (BCR) sequential extraction procedure to get more information for the reasonable disposal of sludge. Sewage sludge was collected from five municipal wastewater treatment plants and three industrial wastewater treatment plants. The sludge was examined for and the total concentrations and different chemical fractions of Cd, Cr, Pb, Cu, Ni and Zn. The total metal concentrations of heavy metals in sludge varied greatly. The contents of Zn and Cu were the highest, followed by then Cr, Ni and Pb and the content of Cd was the least. There was no significant difference in total metal concentration between municipal and industrial wastewater treatment plants. Fractions extracted by the BCR sequential procedure were acid soluble/exchangeable, reducible and oxidizable fraction. Sludge pH was found to have profound effect on the chemical fractions of heavy metals. Acidic sludges (Xiamen and Jinlin Petrochemical Group Co., wastewater treatment plant) had higher proportion of the acid soluble/exchangeable fractions than in neutral sludge. In neutral sludges, Pb and Cr were principally distributed in between the oxidizable fraction and the residual fraction; Cu was in the oxidizable fraction; Cd mainly in the residual fraction in municipal wastewater treatment plants and had high percentage of acid soluble/exchangeable and reducible fractions in industrial wastewater treatment plants; Ni and Zn had higher percentage in the acid soluble/exchangeable and the oxidizable fraction.     

Removal of ammonium ion from aqueous solution using natural Turkish clinoptilolite

A study on ion exchange kinetics and equilibrium isotherms of ammonium ion on natural Turkish clinoptilolite (zeolite) was conducted using a batch experiment technique. The effects of relevant parameters, such as temperature, contact time and initial ammonium (NH(4)(+)) concentration were examined, respectively. The pseudo first-order, pseudo second-order kinetic models and intraparticle diffusion model were used to describe the kinetic data. The pseudo second-order kinetic model provided excellent kinetic data fitting (R(2)>0.990) and intraparticle diffusion effects ammonium uptake. The Langmuir and Freundlich models were applied to describe the equilibrium isotherms for ammonium uptake and the Langmuir model agrees very well with experimental data. Thermodynamic parameters such as change in free energy (DeltaG(0)), enthalpy (DeltaH(0)) and entropy (DeltaS(0)) were also determined. An examination of the thermodynamic parameters shows that the exchange of ammonium ion by clinoptilolite is a process occurring spontaneously and physical in nature at ambient conditions (25 degrees C). The process is also found to be exothermic. The results indicate that there is a significant potential for the natural Turkish clinoptilolite as an adsorbent material for ammonium removal from aqueous solutions.     

Analysis of heavy metals during composting of the tannery sludge using physicochemical and spectroscopic techniques

The major limitation of direct application of tannery sludge compost in agriculture is the total heavy metal contents and their bioavailability to the soil-plant system. This study focused on the heavy metal characterization and the influence of changing the physicochemical properties of the medium throughout the composting on the concentrations, bioavailability or chemical forms of Cr, Cu, Zn, Pb and Cd in tannery sludge. The study shows that throughout the 60 days of composting, physicochemical analysis and Fourier-transformed infrared (FTIR) spectroscopic characterization show that all parameters elaborated and reached relatively stable levels reflecting the stability and maturity of the final product, and revealed the biodegradation of components that can be easily assimilated by microorganism. The C/N ratio reaches the optimal range of stable compost; inorganic nitrogen is transformed into stable organic forms. The total concentration of Cr, Zn, Cu, Pb and Cd is very low rendering final compost acceptable for agricultural use. The germination index for both Chinese cabbage and lettuce was 97% after 60 days of composting, showing that the final compost was not phytotoxic. Furthermore, in using a sequential extraction method in sludge compost at different phases of treatment, a less than 2% of metals bound to bioavailable fractions X-(KNO(3)+H(2)O). A large proportion of the heavy metals were associated to the residual fraction (75-85%) and more resistant fractions to extraction X-NaOH, X-EDTA, X-HNO(3) (15-25%). Mobile fractions of metals are poorly predictable from the total content. Bioavailability of all fractions of elements tends to decrease.     

Effect of dietary clinoptilolite or zeolite NaA on body weight gain and feed ulilization of growing lambs fed urea or intact protein as a nitrogen supplement

Fifty-four growing male lambs were assigned randomly to nine diets in a 3 × 3 factorial arrangement of treatments to determine the effect of dietary clinoptilolite or zeolite NaA on growth, feed utilization and concentrations of several nitrogen and ionic constituents in blood plasma and of selected elements in body tissues. The treatments consisted of a basal (low protein) diet containing no nitrogen supplement (corn, 86%; alfalfa, 12.5% plus vitamins and minerals), and similar diets fortified with urea as a non-protein-N source or with soybean meal as an intact protein source added to the diet isonitrogenously with urea, all fed for 9 weeks. Either clinoptilolite or zeolite NaA was added to each of these three diets at 3% at the expense of corn. Mean daily weight gain was depressed during the first 4 weeks and at 9 weeks in lambs fed diets containing corn or urea when clinoptilolite or zeolite NaA was added (P < 0.05). However, when clinoptilolite was added to the corn-soybean meal diet therewas no growth depression at either 4 or 9 weeks and when zeolite NaA was added, daily gain was improved 21% (307 vs. 372 g) at week 4, but the advantage disappeared by 9 weeks (367 vs. 374 g). Neither clinoptilolite nor zeolite NaA affected plasma concentrations of protein, Ca, P, Mg, Na or K at 9 weeks. The pH of the gastrointestinal tract contents was not affected, except for an increase in pH of cecal contents due to clinoptilolite and zeolite NaA. There was no evidence of changes in liver, kidney, testes and muscle concentrations of major or minor elements in lambs fed clinoptilolite or zeolite NaA. Growth and feed utilization of lambs fed soybean meal were greater than for lambs fed urea; the response to dietary zeolites appears to be related to dietary nitrogen level and source in lambs.     

Sorption processes and XRD analysis of a natural zeolite exchanged with Pb(2+), Cd(2+) and Zn(2+) cations

In this study the Pb(2+), Cd(2+) and Zn(2+) adsorption capacity of a natural zeolite was evaluated in batch tests at a constant pH of 5.5 by polluting this mineral with solutions containing increasing concentrations of the three cations to obtain adsorption isotherms. In addition X-ray powder diffraction (XRD) was used to investigate the changes of zeolite structure caused by the exchange with cations of different ionic radius. The zeolite adsorption capacity for the three cations was Zn>Pb>Cd. Moreover a sequential extraction procedure [H(2)O, 0.05 M Ca(NO(3))(2) and 0.02 M EDTA] was applied to zeolite samples used in the adsorption experiments to determine the chemical form of the cations bound to the sorbent. Using this approach it was shown that low concentrations of Pb(2+), Cd(2+) and Zn(2+) were present as water-soluble and exchangeable fractions (<25% of the Me adsorbed), while EDTA extracted most of the adsorbed cations from the zeolite (>27% of the Me adsorbed). The XRD pattern of zeolite, analysed according to the Rietveld method, showed that the main mineralogical phase involved in the adsorption process was clinoptilolite. Besides structure information showed that the incorporation of Pb(2+), Cd(2+) and Zn(2+), into the zeolite frameworks changed slightly but appreciably the lattice parameters. XRD analysis also showed the occurrence of some isomorphic substitution phenomena where the Al(3+) ions of the clinoptilolite framework were replaced by exchanged Pb(2+) cations in the course of the ion exchange reaction. This mechanism was instead less evident in the patterns of the samples doped with Cd(2+) and Zn(2+) cations.     

Release of Zn, Ni, Cu, SO4(2-) and CrO4(2-) as a function of pH from cement-based stabilized/solidified refinery oily sludge and ash from incineration of oily sludge

A framework for the evaluation of leaching behavior of inorganic constituents from stabilized/solidified refinery oily sludge and ash produced from incineration of oily sludge with cement was employed. Metal and anion release as a function of pH was investigated. The leaching test consisted of multiple parallel extractions at pH range from 2 to 12. Remarkably good immobilization >98% was observed for metals of solidified ash at pH>6 and >93% of solidified oily sludge at pH>7. Sulfate leaching was high at pH range 2-12. The leaching behavior of metals and anions was simulated by VMINTEQ. The calculations showed that leaching behavior of Zn, Ni and Cu was controlled by chemical equilibrium and surface complexation onto ferrihydrite, at the pH range 2-12. The dominant solid phases that controlled metal leachability were metal hydroxides. The dominant mechanism that described sulfate leaching was found to be chemical equilibrium. Sulfate and also chromate leachability was controlled by Ettringite and Cr(VI)Ettringite as the major minerals affecting their release.     

Evaluation of the effectiveness of various amendments on trace metals stabilization by chemical and biological methods

We evaluated the effects of five different kinds of amendments on heavy metals stabilization. The five amendments were: zero valent iron, limestone, acid mine drainage treatment sludge, bone mill, and bottom ash. To determine bioavailability of the heavy metals, different chemical extraction procedures were used such as, extraction with (Ca(NO(3))(2), DTPA; toxic characteristic leaching procedure (TCLP), physiologically based extraction test (PBET) that simulates gastric juice, and sequential extraction test. Bioavailability was also determined by measuring uptake of the heavy metals by lettuce (Lactuca sativa L.) and earthworms (Eisenia fetida). In addition, dehydrogenase activity was measured to determine microbial activity in the soil with the different amendments. The addition of amendments, especially limestone and bottom ash, resulted in a significant reduction in extractable metal contents. Biological assays using lettuce, earthworm, and enzyme activity were found as appropriate indicators of available metal fraction after in situ stabilization of heavy metals. In conclusion, TCLP and sequential extraction test appear to be promising surrogate measure of metal bioavailability in soils for several environment endpoints.     

Extraction kinetics of heavy metal-containing sludge

In order to remove and recover copper, zinc, cadmium, and chromium from the wastewater treatment sludge generated by an electroplating process, the heavy metal extraction kinetics was studied in a batch reactor using two different extraction agents (nitric and citric acid) at constant agitation speed (150 rpm) and solid to liquid ratio (10 g/L), but varying acid concentrations (0.02-0.10 N), temperatures (25-85 degrees C in nitric acid solution, 25-95 degrees C in citric acid solution), and sludge particle sizes. The shrinking-core model and empirical kinetic model were adopted to analyze the experimental data. Although both models could fit the experimental kinetic data well, the obtained parameters of the shrinking-core model did not show reasonable trends varying with the experimental variables while the empirical model parameters showed significant trends. The experimental and modeling results showed that the metal extraction rates increased with acid concentration, temperature, but decreased with increasing particle size. Nitric acid was found to be more effective than citric acid to extract the heavy metals from the sludge. The extraction activation energies obtained in this study suggested that both a physical diffusion process and a chemical reaction process might play important roles in the overall extraction process.     

沸石粉体对胆固醇型人体胆结石体外吸附研究

为研究沸石粉体对胆固醇型人体胆结石体外吸附的可能性,采用SEM观察了胆固醇型人体胆结石的表面形貌;利用IR对其化学组成进行了分析,并根据天然斜发沸石所具有的较强吸附性能,分别研究了天然沸石粉体和盐酸活化沸石粉体对胆固醇型人体胆结石的体外吸附行为。结果表明:在体外环境下两种沸石对胆固醇型人体胆结石均有一定的吸附能力,但后者吸附效果较前者差,其吸附机理有待进一步深入研究。     

Study of speciation of metals in an industrial sludge and evaluation of metal chelators for their removal

Leachability and mobility of metals were evaluated in sludge obtained from electroplating industry, using toxicity characteristic leaching procedure (TCLP) and diethylene triamine pentaacetic acid test (DTPA). Sequential leaching procedure was used to determine the chemical fractionation of metals. Further, removal of metals from sludge using various chelators (EDTA, citric acid, siderophore) was evaluated. The leaching test indicated that nickel in the sludge sample exceeded 5 ppm concentration. This categorized the sludge, as a toxic waste. The mobility of the metals in the sludge was in the following order: Ni, Fe, Zn, Cr, Pb. Metals were found to be associated with various fractions of sludge. The metal concentration in the sludge was very high as compared to normal abundance and thus not within the range to be used as a fertilizer. The low removal of metals from the sludge by various chelators may be due to overloading of metals and use of aged sludge rather than artificially contaminated one for the study. The results of this study bring forth the prospect of the use of siderophores for bioremediation, because it is biodegradable and ecofriendly. This can be achieved with further optimization of the method, exploration of more potent siderophores and by inclusion of metal bound sludge fraction specific treatments.     

Heavy metal speciation and leaching behaviors in cement based solidified/stabilized waste materials

A circuit board printing factory sludge containing high concentrations of copper, zinc and lead was stabilized and solidified (S/S) with different portions of ordinary Portland cement (OPC) and pulverized fly ash (PFA). The chemical speciation and leaching behavior of heavy metals in these cement-based waste materials were studied by different sequential extraction procedures, standard toxicity characteristic leaching procedure (TCLP) and progressive TCLP tests. The sequential extraction results showed that more than 80% of Cu, Pb and Zn were associated with Fraction 2 (weak acid soluble, extracted with 1M NaOAc at pH 5.0 with a solid to liquid ratio of 1:60). This indicated that the heavy metals could exist in the S/S matrix as metal hydrated phases or metal hydroxides precipitating on the surface of calcium silicate hydrates (C-S-H), PFA and sludge particles. The progressive TCLP test results and MINTEQA2 calculation also showed the importance of Cu and Zn oxides during the leaching process. The leaching behaviors of these metals in the S/S waste materials were mainly controlled by the alkaline nature and acid buffering capacity of the S/S matrix. During the progressive TCLP tests, the alkaline conditions and acid buffering capacity of the matrix decreased with the dissolution of calcium hydroxide and C-S-H, therefore, the leaching of heavy metals in the S/S waste materials increased. The leaching of heavy metals in the S/S materials can be considered as a pH dependent and corresponding metal hydroxide solubility controlled process.     

Influence of pH, curing time and environmental stress on the immobilization of hazardous waste using activated fly ash

The current work is related to inorganic species in sludge generated from Common Effluent Treatment Plant contaminated with hazardous wastes at relatively high concentration. The environmental sensitive metals studied in the sludge are Pb, Fe, Ni, Zn and Mn. The solidification/stabilization (S/S) of heavy metals within fly ash-cement-based matrix was conducted for low cost treatment and reuse of sludge. The study examines the strength of the S/S product by predicting the effect of supplementary cementing material from efficiency factor (k) at 60 degrees C curing temperature. The leaching test was performed at two different pH 7 and 4 to determine the efficiency of heavy metal immobilization. It was observed that replacing 76% OPC by 56% fly ash and 20% sludge for 28 days curing period shows increase in strength as well as rate of stabilization for zinc, iron and manganese at pH 7, lead and nickel were stabilized by 79 and 82%, respectively. Environmental stress test was performed to evaluate the tolerance of extreme adverse environmental condition.     

Biosorption of nickel from protonated rice bran

In the present study biosorption technique, the accumulation of metals by biomass was used for the removal of nickel from aqueous medium. The rice bran in its acid treated (H(3)PO(4)) form was used as a low cost sorbent. The adsorption characteristics of nickel on protonated rice bran were evaluated as a function of pH, biosorbent size, biosorbent dosage, initial concentration of nickel and time. Within the tested pH range (pH 1-7), the protonated rice bran displayed more resistance to pH variation, retaining up to 102 mg/g of the nickel binding capacity at pH 6. Meanwhile, at lower pH values the uptake capacity decreased. The % age removal of nickel was maximum at 0.25 g of biosorbent dose and 0.25 mm biosorbent size. At the optimal conditions, metal ion uptake was increased as the initial metal ion concentration increased up to 100mg/L. Kinetic and isotherm experiments were carried out at the optimal pH 6.0 for nickel. The metal removal rate was rapid, with 57% of the total adsorption taking place within 15-30 min. The Freundlich and Langmuir models were used to describe the uptake of nickel on protonated rice bran. The Langmuir and Freundlich model parameters were evaluated. The equilibrium adsorption data was better fitted to Langmuir adsorption isotherm model. The adsorption followed pseudo second-order kinetic model. The thermodynamic assessment of the metal ion-rice bran biomass system indicated the feasibility and spontaneous nature of the process and DeltaG degrees values were evaluated as ranging from -22.82 to -24.04 kJ/mol for nickel sorption. The order of magnitude of the DeltaG degrees values indicated an ion-exchange physiochemical sorption process.     

Galvanic sludge metals recovery by pyrometallurgical and hydrometallurgical treatment

This paper reports a study, on laboratory scale, of sulphating roasting to perform a treatment for a selective recovery of valuable metals from galvanic sludge. The target metals were copper, zinc and nickel and the sulphating agent used was pyrite, from coal wastes. The particularity of this treatment is the use of two hazardous wastes as raw material. They are generated in large quantities at coal extraction sites (coal wastes) and at plating shops (galvanic sludge). The wastes were characterized by X-ray fluorescence (XRF), particle size distribution and water contents. The chemical characterization showed sludges with high copper concentration, with more than 14% (dry base). In the roasting step, the galvanic sludge was mixed with pyritic waste and the parameters evaluated were galvanic sludge/pyrite ratio, roasting temperature and roasting time. After roasting, the product of reaction was leached with water in room temperature for 15 min. Considering that other studies have already demonstrated that the pyrometallurgical step determines the process efficiency, this paper only reports the influence of pyrometallurgical parameters. Hydrometallurgical processes will be better evaluated in further studies. The conditions that best reflect a compromise between the valuable metal recover and the economical viability of the process were achieved for 1:0.4 galvanic sludge/pyrite ratio, 90 min of roasting time and 550 degrees C of roasting temperature. These conditions lead to a recovery of 60% zinc, 43% nickel and 50% copper.     

Treatment of radioactive liquid waste by sorption on natural zeolite in Turkey

Liquid radioactive waste has been generated from the use of radioactive materials in industrial applications, research and medicine in Turkey. Natural zeolites (clinoptilolite) have been studied for the removal of several key radionuclides ((137)Cs, (60)Co, (90)Sr and (110m)Ag) from liquid radioactive waste. The aim of the present study is to investigate effectiveness of zeolite treatment on decontamination factor (DF) in a combined process (chemical precipitation and adsorption) at the laboratory tests and scale up to the waste treatment plant. In this study, sorption and precipitation techniques were adapted to decontamination of liquid low level waste (LLW). Effective decontamination was achieved when sorbents are used during the chemical precipitation. Natural zeolite samples were taken from different zeolite formations in Turkey. Comparison of the ion-exchange properties of zeolite minerals from different formations shows that Gordes clinoptilolite was the most suitable natural sorbent for radionuclides under dynamic treatment conditions and as an additive for chemical precipitation process. Clinoptilolite were shown to have a high selectivity for (137)Cs and (110m)Ag as sorbent. In the absence of potassium ions, native clinoptilolite removed (60)Co and (90)Sr very effectively from the liquid waste. In the end of this liquid waste treatment, decontamination factor was provided as 430 by using 0.5 mm clinoptilolite at 30 degrees C.