Stabilization of heavy metals in ceramsite made with sewage sludge

In order to investigate stabilization of heavy metals in ceramsite made with sewage sludge as an additive, the configuration of heavy metals in ceramsite was analysed by XRD and while leaching tests were conducted to find out the effect of sintering temperature (850 degrees C, 900 degrees C, 950 degrees C, 1000 degrees C, 1100 degrees C, and 1200 degrees C), pH (1, 3, 5, 7, 9, and 12), and H2O2 concentration (0.5molL(-1), 1molL(-1), 1.5molL(-1), 3molL(-1), and 5molL(-1)) on stabilization of heavy metals (Cd, Cr, Cu, and Pb) in ceramsite. The results indicate that leaching contents of heavy metals do not change above 1000 degrees C and sintering temperature has a significant effect on stabilization of heavy metals in ceramsite; leaching contents of heavy metals decrease as pH increases and increase as H2O2 concentration increases. XRD analysis reveals that the heavy metals exist in steady forms, mainly Pb2O(CrO(4)), CdSiO3, and CuO at 1100 degrees C. It is therefore concluded that heavy metals are properly stabilized in ceramsite and cannot be easily released into the environment again to cause secondary pollution.     

Influence of brown coal on limit of phytotoxicity of soils contaminated with heavy metals

The paper gives knowledge and application values in efficiency of applying brown coal to limit uptake of heavy metals from contaminated soils by different plant species. The paper determines possibility and principles of using brown coal in reclamation of soils contaminated with heavy metals and rebuilding soils on devastated terrains like terrain in the influence zone of Copper-Smelter "Legnica". On the basis of pot experiment it was stated that increasing doses of brown coal limited phytotoxicity of soils. Results of the paper show that tested fertilizer could be applied on soils strongly contaminated with heavy metals giving long-lasting improvement of reclaimed soils.     

Evaluation of electrokinetic removal of heavy metals from sewage sludge

The presence of heavy metals is one of the main obstacles for agricultural use of million tonnes of dewatered sewage sludge produced in wastewater treatment plants. Electrokinetic (EK) treatment can be applied to remove heavy metals from sludge. The aim of this study was to increase the efficiency of electrokinetic removal of heavy metals from dewatered sewage sludge. EK experiments were carried out with and without pH adjustment in cathode chamber of acidified sewage sludge. The selective sequential extraction (SSE) was used to determine the fractionation of heavy metals in sewage sludge. The mobility of heavy metals in sludge significantly increased after its acidification at pH 2.7 and followed the order: Ni, Zn, Cu, As, Cr, Pb. Removal efficiencies of heavy metals in the experiment with acidified sewage sludge and pH adjustment at cathode chamber at 2.0 were: 95% for Zn, 96% for Cu, 90% for Ni, 68% for Cr, 31% for As and 19% for Pb. The concentrations of Zn, Cu, Ni, Cr and Pb after EK treatment were below the United States Environmental Protection Agency limits for biosolids applied to agricultural land, forest, public contact sites or reclamation sites.     

Inhibitory effect of heavy metals on methane-producing anaerobic granular sludge

Heavy metals could potentially have a negative impact on methane-producing anaerobic granular sludge. The objective of this study was to investigate the inhibitory effect of zinc(II), chromium(VI), nickel(II), and cadmium(II) on the methane-producing activity of granular sludge sampled from the upflow anaerobic sludge blanket reactor that treats the wastewaters of a yeast factory, for a range of concentrations between 0 and 128 mg L(-1). The modified Gompertz, Logistic, and Richards equations were applied to describe the inactivation of anaerobic culture by heavy metals. According to these models, the values of methane production potential (mL) for a heavy metal concentration of 128 mg L(-1) were in the following order: Ni (44.82+/-0.67)>Cd (28.73+/-0.11)>Cr (15.52+/-1.63)>Zn (0.65+/-0.00). The IC(50) values, the metal concentrations that cause a 50% reduction in the cumulative methane production over a fixed period of exposure time (24h), for the individual heavy metals were found to be in the following order: Zn (most toxic; 7.5 mg L(-1))>Cr (27 mg L(-1))>Ni (35 mg L(-1)) approximately Cd (least toxic; 36 mg L(-1)).     

Adsorption of heavy metals from wastewater with waste activated sludge

Abstract

The purpose of this study is the investigation of the adsorption of heavy metals from wastewater with waste activated sludge (WAS) so as to increase the operational flexibility of activated sludge processes for the shock loading problems of heavy metals. By contacting the raw wastewater with WAS, before it entered the activated sludge process unit, some heavy metals in the wastewater were removed, and the pH value of the acidic wastewater rose. Five metals, Cu, Zn, Ni, Cd and Pb, were studied, some factors which affected this biosorption phenomena were investigated, and expressions of the adsorption isotherms were discussed. A semi‐empirical mass transfer‐adsorption model was developed to describe the kinetic experimental data.     

Solvent extraction applied to the recovery of heavy metals from galvanic sludge

In this study, a hydrometallurgical treatment involving the solvent extraction and recovery of some heavy metals from a sulphuric acid leach solution of galvanic sludge, using di-(2-ethylhexyl)-phosphoric acid (D2EHPA) and bis-(2,4,4-trimethylpentyl)-phosphinic acid (Cyanex 272), both diluted in kerosene, has been investigated.

The preliminary tests revealed the necessity to remove other metal species than zinc and nickel, contained in the leach solution, and therefore, processes to cement copper and precipitate chromium were then applied to finally obtain a Zn and Ni pregnant solution prior to solvent extraction. For the experimental conditions studied, Cyanex 272 showed a good recovery of Zn after the stripping stage using H₂SO₄, but D2EHPA effectively promoted a higher Zn extraction than Cyanex 272 did. The dependence of the solvent extraction method on variables such as pH, contact time and concentration of extractant, as well as the effect of different concentrations of sulphuric acid on stripping, are discussed.

The discussion also includes the previous conditions developed to separate the main interfering metallic species from the leach solution in order to improve the extraction and recovery of zinc by solvent extraction. The final objective has been to achieve a solution as pure as possible to recover nickel sulphate.     

Distribution of extractable fractions of heavy metals in sludge during the wastewater treatment process

Sludge samples were collected from different treatment steps of Gaobeidian wastewater treatment plant (WWTP) of Beijing City, PR China, to investigate the distributions of total and chemical fractions of Fe, Mn, Ni, Cu, Zn, Cr, Pb, and Mo in different sludges. The highest total concentrations were found for Fe, Mn, Pb, and Mo in digested sludge (DS), Ni and Cr in thickened sludge (TS), Zn in dewatering sludge (DWS), and Cu in active sludge (AS). The lowest concentrations were observed in AS, except for Cu in TS. Significant differences of total metal concentration were observed between AS and TS (or DS), suggesting that sludge thickening and digesting treatments significantly influenced the total metal concentrations. Fe, Cu, Ni, Cr, Mo, and Pb distributed principally in the residual fraction in all sludges, while Zn and Mn presented in a highly available fraction. For same metal in different sludges, the portion of easily mobile fraction decreased significantly along the wastewater treatment process, and metals in AS presented in the highest available fraction. Organic matter contents, TN, and TP of sludges exhibited a significant positive correlation with the concentrations of exchangeable and reducible fraction of Pb, Mo, Cr, Cu, and Fe, while sludge pH demonstrated significant negative correlations with the concentrations of these metals.     

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.     

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.     

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.     

Speciation of heavy metals in untreated sewage sludge by using microwave assisted sequential extraction procedure

A fast microwave assisted extraction procedure was developed and optimized for their eventual exploitation in the three-stage sequential extraction procedure proposed by modified BCR protocol (the community Bureau of Reference now the European Union "Measurement and Testing Programme"). The effects of the microwave treatment on the extraction of Cd, Cr, Cu, Ni, Pb and Zn from untreated sewage sludge collected from Hyderabad city (Pakistan) were compared with those obtained from sequential BCR extraction procedure. In sequential BCR method, each extraction step takes 16 h, where as with the use of compromised microwave conditions, extraction steps could be completed in about 120 s, for each step, respectively. Extractable Cd, Cr, Pb and Ni obtained by both comparable methodologies were measured by electrothermal atomic absorption spectrometry (ETAAS), while for Cu and Zn flame atomic absorption spectrometry (FAAS) was used. The validations of both extraction techniques were compared by the analysis of certified reference material of soil amended with sewage sludge (BCR 483). The results of the partitioning study of untreated waste water sewage sludge, indicate that more easily mobilized forms (step 1) were predominant for Cd, Ni and Zn (28.3, 28.4 and 43.7%), in contrast, the largest amount of Cd and Pb (66.4 and 72.8%) was associated with the iron/manganese oxide while Cr and Ni (71.2 and 38.7%) in organic matter/sulphide fractions. The overall metal recoveries in steps 1-3 (excluding residual step) were 95.3-104% of those obtained with the sequential BCR protocol. The accuracy of the proposed microwave extraction method (expressed as %R.S.D.) was lower than 10% for all metals.     

The distribution of heavy metals during fluidized bed combustion of sludge (FBSC)

During combustion of wastewater treatment sludge, the inorganic constituents are converted into ash which contains the major fraction of the heavy metals present. The behaviour of heavy metals in combustion processes has been studied extensively for mostly coal combustion and waste incineration. For biomass and sludge, literature data are scarce and mostly limited to laboratory experiments. The present paper assesses the partitioning of eight heavy metals (Hg, As, Cd, Cu, Pb, Cr, Ni and Zn) in the different residues from a large-scale fluidized bed sludge combustor of 4.4 m i.d. The origin of the sludge is mostly from treating urban wastewaters (>90%), although some mixed sludge (urban+industrial, <10%) is also burnt. The different residues (bottom ash, fly ash, filter cake, scrubber effluent and stack emissions) were sampled and analysed during 33 weeks, spread over a period of 1 year. The mass balance of relevant heavy metals closes for 96.5%, inaccuracies being related to the unsteadiness of the process, the accuracy of the mass flow data monitored at the plant, and on collecting representative samples. It is also shown that all heavy metals under scrutiny, except Hg, are concentrated in the fly ash as collected in the electrostatic precipitator.     

Improvement of dewatering capacity of a petrochemical sludge

Oily sludge produced from a petrochemical industry was used to investigate the improvement of its dewatering properties. The oil content (OC) and the dry solid content (DS) of the raw sludge were respectively, 15% and 3.6% by weight. The capillary suction time (CST) and the specific resistance to filtration (SRF) of the raw petrochemical industrial sludge were found to be 2000s and approximately 5.5x10(16)m/kg, respectively. Conventional chemical conditioners such as alum, lime, and polyelectrolyte, and less conventional ones like fly ash, gypsum, and bentonite were used in the sludge conditioning studies. Conventional chemical conditioners gave better results for the enhancement of the dewatering capacity of the sludge. The best result was obtained by using 0.9% cationic polyelectrolyte by weight, and a decrease of 99%-95% were achieved for CST and SRF, respectively, when this dosage of cationic polyelectrolyte was used.     

Effect of metal spiking on different chemical pools and chemically extractable fractions of heavy metals in sewage sludge

A laboratory experiment was conducted to study the effect of metal spiking and incubation on some properties and sequentially extractable chemical pools of some heavy metals (F1, two extractions with 0.1 M Sr(NO3)2; F2, one extraction with 1 M NaOAc (pH 5.0); F3, three extractions with 5% NaOCl (pH 8.5) at 90-95 degrees C; F4, three extractions with 0.2 M oxalic acid + 0.2 M ammonium oxalate + 0.1 M ascorbic acid (pH 3.0); and F5, dissolution of sample residue in HF-HClO4 (residual fraction,) and also 1 M CaCl2 and 0.005 M DTPA extractable heavy metals in sewage sludge. Metal spiking and incubation decreased pH and easily oxidizable organic C content of sludge but increased electrical conductivity. Metal spiking and incubation increased F1 fraction of all heavy metals, F2 fraction of Ni, Pb, Cu, and Cd, F3 fraction of Pb, Cu, and Cd, F4 or reducible fraction of Ni, Cu, and Cd and residual fraction of Zn and Pb, but decreased F2 fraction of Zn, F3 of Zn and Ni, F4 fraction of Zn and F5 fraction of Ni, Cu, and Cd. Metal spiking and incubation increased 1 M CaCl2 and 0.005 M DTPA extractable amounts of all heavy metals in sludge except for 0.005 M DTPA extractable Zn, which registered only very marginal decrease.     

Effect of acclimatization of microorganisms to heavy metals on the performance of activated sludge process

Although selected heavy metals (HMs) stimulate biological reactions at low concentrations, all HMs are toxic to microorganisms (MOs) at moderate concentrations and can cause inhibitory effects on the biological processes. Therefore, MOs must be acclimated to HMs or other toxic substances present in wastewaters (WWs) before they are used in an activated sludge process (ASP). In this study, combined effect of Cu(2+) and Zn(2+) ions in a synthetic WW on the efficiency of a laboratory-scale ASP without recycle was investigated using acclimated MOs at different extents.A synthetic feed solution of 1222 mg L(-1) proteose-peptone (corresponding to 1300 mg COD L(-1)) served as a source of carbon. Cu(2+) and Zn(2+) ions at different concentrations (1.5, 4.5 and 9, 27 mg L(-1), respectively) were introduced in the feed to a continuously stirred activated sludge reactor at different hydraulic residence times (2-40 h) keeping pH, temperature and stock feed composition constant. The combined effects of copper and zinc ions were determined by mixing these metallic ions at the specified combinations of concentrations such as "1.5 mg L(-1) of Cu(2+)+9 mg L(-1) of Zn(2+)" and "4.5 mg L(-1) of Cu(2+)+27 mg L(-1) of Zn(2+)". It was observed that using seed MOs acclimatized to two times of the combined threshold concentration of these HMs for an unduly long period of time (1-4 months) caused adverse effects on the ASP performance. Besides, it was found that usual inhibition effects of these HMs were enhanced with increasing period of acclimation. Substantially lower substrate removal efficiencies were obtained with acclimatized MOs than those obtained with non-acclimatized MOs. At the higher initial substrate concentration of 2500 mg COD L(-1), substrate-inhibition occurred causing a decrease in the specific growth rate constant (k); however, HM inhibition was suppressed, resulting to about 20% increase in treatment efficiency of the ASP. It can be concluded that the time period necessary for acclimatization of seed MOs must be adjusted carefully with concentrations of HMs lower than their threshold concentrations to achieve an optimal operation of an aerobic biological process.     

膜分离技术在石油化工领域中的应用

通过分析气体膜分离、渗透汽化膜分离和膜生物反应器等膜技术在石化领域中的应用 ,提出应开发高性能的膜材料和膜、膜装置及过程优化 ,以及膜分离与其他分离技术耦合的必要性。