Metal sorption on soils as affected by the dissolved organic matter in sewage sludge and the relative calculation of sewage sludge application

To evaluate the influences of sewage sludge-derived organic matters on metal sorption and on the resultant sludge loading estimates, a batch experiment was conducted to compare the sorption of Ni, Cu and Pb in sewage sludge filtrates (1:20 sewage sludge to water) on eight soils and the adsorption of metals in a reference solution which had the same matrix as the sewage sludge filtrate except dissolved organic material (henceforth referred to as reference solution). Metal sorption could be well fitted by linear isotherm and the dissolved organic matter in sludge significantly depressed the sorption (p<0.01). The main factor controlling sorption of Ni on different soils was dominated by soil cation exchange capacity (CEC) and sorption of Cu and Pb was by soil organic matter (SOM). The parameters obtained from the sorption isotherm equations were then used to estimate sludge loadings into the soils. When the sorption parameters derived from the reference solution were used for calculation, that is the effect of dissolved organic matter was not considered, the calculated safe application rates are approximately 47.8, 51.4, 34.2, 31.3, 21.7, 46.3, 187.1 and 27.6 t-sludge/ha for the Beijing, Jiangxi, Xiamen, Jilin, Guangdong, Wuhan, Gansu and Xinjiang soils, respectively. However, when the sorption parameters derived from the dissolved organo-metallic complexes are used for calculation, the corresponding application rates are reduced to approximately 6.0, 3.4, 1.9, 10.0, 6.3, 3.6, 7.3 and 3.5 t-sludge/ha, respectively. By this study we can get a conclusion that the effect of sewage sludge derived dissolved organic matter on heavy metal sorption and soil properties should be considered in the course of regulating the safe application rates of sewage sludge to soil.     

Stabilization treatment of soft subgrade soil by sewage sludge ash and cement

In this study, incinerated sewage sludge ash (ISSA) is mixed with cement in a fixed ratio of 4:1 for use as a stabilizer to improve the strength of soft, cohesive, subgrade soil. Five different ratios (in wt%: 0%, 2%, 4%, 8%, and 16%) of ISSA/cement admixture are mixed with cohesive soil to make soil samples. In order to understand the influences of admixtures on the soil properties, tests of the pH value, Atterberg limits, compaction, California bearing ratio (CBR), unconfined compressive strength, and triaxial compression were performed on those samples. The study shows that the unconfined compressive strength of specimens with the ISSA/cement addition was improved to approximately 3-7 times better than that of the untreated soil; furthermore, the swelling behavior was also effectively reduced as much as 10-60% for those samples. In some samples, the ISSA/cement additive improved the CBR values by up to 30 times that of untreated soil. This suggests that ISSA/cement has many potential applications in the field of geotechnical engineering.     

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.     

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.     

Treatment of sewage sludge using electrokinetic geosynthetics

The treatment and disposal of sewage sludge is one of the most problematical issues affecting wastewater treatment in the developed world. The traditional outlets for sewage sludge are to spread it on agricultural land, or to form a cake for deposit to landfill or incineration. In order to create a sludge cake, water must be removed. Existing dewatering technology based on pressure can only remove a very limited amount of this water because of the way in which water is bound to the sludge particles or flocs. Several researchers have shown that electrokinetic dewatering of sludge is more efficient than conventional hydraulically driven methods. This involves the application of a dc voltage across the sludge, driving water under an electrical gradient from positive (anode) electrode to negative (cathode) electrode. However, there have been several reasons why this technique has not been adopted in practice, not least because the, normally metallic, anode rapidly dissolves due to the acidic environment created by the electrolysis of water. This paper will describe experimentation using electrokinetic geosynthetics (EKG): polymer-based materials containing conducting elements. These have been used to minimise the problem of electrode corrosion and create a sludge treatment system that can produce dry solids contents in excess of 30%. It will suggest different options for the treatment of sludges both in situ in sludge lagoons and windrows, and ex situ as a treatment process.     

Adsorption of copper(II) onto sewage sludge-derived materials via microwave irradiation

The materials with adsorbent properties were produced from urban sewage sludge by two different procedures via microwave irradiation: (1) by one single pyrolysis stage (SC); (2) by chemical activation with ZnCl₂ (SZ). The BET, SEM and FT-IR have been used to evaluate the pore structural parameters and surface chemistry of the adsorbents, respectively. Subsequently they were used for adsorption of Cu(II) from aqueous solutions. The effects of various experimental parameters, such as pH, temperature were investigated in a batch-adsorption technique. The results showed that the adsorption of Cu(II) was maximal at pH 5.0. The kinetic study demonstrated that the adsorption process was followed the second-order kinetic equation. The experimental adsorption isotherm data were well fitted with Langmuir model and the maximum adsorption capacity of Cu(II) were found to be 3.88 and 10.56 mg/g for SC and SZ, respectively, in the solution of pH 5.0. Thermodynamic parameters such as changes in the enthalpy (ΔH⁰), entropy (ΔS⁰) and free energy (ΔG⁰) indicate that Cu(II) adsorption onto SC and SZ is an endothermic and spontaneous process in nature at 15-45 °C. These results indicate that the sewage sludge-derived material via microwave induced ZnCl₂ activation is an effective and alternative adsorbent for the removal of Cu(II) from aqueous solution.     

Co-combustion of coal and sewage sludge: Chemical and ecotoxicological properties of ashes

The co-combustion of sewage sludge (SS) and coal is widely used for the treatment and thermal valorization of SS produced in wastewater treatment plants. The chemical and ecotoxicological properties of the ashes produced in this thermal treatment have not been fully studied. Two combustion tests were performed in a fluidized bed combustor. Colombian coal was used as fuel in test A. A blend (1 + 1) of this coal and a stabilized SS (Biogran^®) was used in a second test B. Samples of the bottom and fly ashes trapped in two sequential cyclones were collected. The characterization of the ashes was focused on two main aspects: (1) the bulk content of a set of metals and (2) the characterization of eluates produced according to the European Standard leaching test EN 12457-2. The eluates were submitted to an ecotoxicological characterization for two bio-indicators. In what concerns the bulk content of ashes, both combustion tests have produced ashes with different compositions. The ashes formed during the co-combustion test have shown higher concentrations of metals, namely Cr, Cu, Ni, Pb, Zn and Fe for all ashes. The leaching test has shown low mobility of these elements from the by-products produced during the combustion and co-combustion tests. Cr and Cr(VI) were mainly detected in the eluates of the 1st cyclone ashes produced in both combustion tests and in the 2nd cyclone ashes produced in the co-combustion test.Considering the ecotoxicity assays, the eluates of bottom and fly ashes for both combustion and co-combustion tests have shown low ecotoxic levels. The micro-crustacean Daphnia magna was generally more sensitive than the bacterium Vibrio fischeri. CEMWE criterion has allowed to classify the bottom ashes for both combustion and co-combustion tests as non-toxic residues and the fly ashes collected in both cyclones as toxic.     

Microwave enhanced stabilization of heavy metal sludge

A microwave process can be utilized to stabilize the copper ions in heavy metal sludge. The effects of microwave processing on stabilization of heavy metal sludge were studied as a function of additive, power, process time, reaction atmosphere, cooling gas, organic substance, and temperature. Copper leach resistance increased with addition of aluminum metal powder, with increased microwave power, increased processing time, and using a gaseous environment of nitrogen for processing and air for cooling [N2/air]. The organic in the sludge affected stabilization, whether or not the organic smoldered. During heating in conventional ovens, exothermic oxidation of the organic resulted in sludge temperatures of about 500 degrees C for oven control temperatures of 200-500 degrees C. After microwave heating dried the sludge, the sludge temperature rose to 500 degrees C. The reaction between copper ions and metal aluminum in the dried sludge should be regarded as a solid phase reaction. Adding aluminum metal powder and reaction temperature were the key parameters in stabilizing copper in the heavy metal sludge, whether heated by microwave radiation or conventional oven. The mass balance indicates insignificant volatization of the copper during heating.     

Concentration and speciation of heavy metals in six different sewage sludge-composts

This study presents the concentrations and speciation of heavy metals (HMs) in six different composts of sewage sludges deriving from two wastewater treatment plants in China. After 56 days of sludge composting with rice straw at a low C/N ratio (13:1), cadmium (Cd), copper (Cu), lead (Pb) and zinc (Zn) were enriched in sludge composts, exhibiting concentrations that varied from 0.75 to 2.0, 416 to 458, 66 to 168 and 1356 to 1750mgkg(-1) dry weight (d.w.), respectively. The concentrations increased by 12-60% for Cd, 8-17% for Cu, 15-43% for Pb and 14-44% for Zn compared to those in sewage sludges. The total concentrations of individual or total elements in the final composts exceeded the maximum permissible limits proposed for compost or fertilizer. In all the final composts, more than 70% of total Cu was associated with organic matter-bound fraction, while Zn was mainly concentrated in exchangeable and Fe-Mn oxide-bound fractions which implied the high mobility and bioavailability. Continuously aerated composting treatment exhibited better compost quality and lower potential toxicity of HMs, whereas inoculant with microorganism and enzyme spiked during composting had no obvious advantage on humification of organic matter and on reducing HM mobility and bioavailability.     

Vermistabilization of municipal sewage sludge amended with sugarcane trash using epigeic Eisenia fetida (Oligochaeta)

Efforts have been made in this study to stabilize the sewage sludge mixed with sugarcane trash in four different proportions: 20% (T(1)); 40% (T(2)); 60% (T(3)) and 80% (T(4)), under laboratory conditions using epigeic earthworm (Oligochaeta) Eisenia fetida. The composting potential of worm was also evaluated in 100% sewage sludge treatment (T(5)). The changes in chemical properties of substrate was measured at the end. The vermicomposted material showed decrease in organic C (4.8-12.7%) and exchangeable K (3.2-15.3%) content, whereas increase in total N (5.9-25.1%) and available P (1.2-10.9%), exchangeable Ca (2.3-10.9%) and exchangeable Mg (4.5-14.0%) contents. Vermicomposting process caused considerable reduction in concentration of diethylene-triaminepentaacetic acid (DTPA) extractable metals: Cu (4.98-30.5%), Fe (5.08-12.64%), Mn (3.31-18.0%), Zn (2.52-15.90%) and Pb (2.38-20.0%). E. fetida showed the better growth performances in first three treatments (T(1)-T(3)) possibly due to higher content of organic matter (supplied by bulking agent, i.e. sugarcane trash). The earthworm mortality was higher in vermibeds those contained more sludge proportions. Study revealed that vermicomposting might be an efficient technology to convert negligible municipal sewage sludge into value-added products. The feasibility of earthworms to mitigate the metal toxicity and to enhance the nutrient profile might be useful to convert noxious sludge into useful products, at low-input basis.     

A study on removal characteristics of copper from aqueous solution by sewage sludge and pomace ashes

In the present work, the abilities of sewage sludge and pomace ashes to remove copper (Cu(2+)) ions from aqueous solutions are compared. Batch adsorption experiments were performed in order to evaluate the removal efficiency of these materials. Effect of contact time, solution pH, ash concentration and temperature on the removal of Cu(2+) was investigated. The results of batch equilibrium studies showed that the solution pH was the key factor affecting the adsorption characteristics. In general, the amount of Cu removed increased as the solid concentration and pH increased, and then it remained constant over a wide pH region. The adsorption test of applying sewage sludge and pomace ashes into synthetic wastewater revealed that the adsorption data of these materials for copper ions were better fitted to the Langmuir isotherm since the correlation coefficients for the Langmuir isotherm were higher than that for the Freundlich isotherm. The estimated maximum capacities of copper adsorbed by sewage sludge and pomace ashes were 5.71 and 6.98 mg g(-1), respectively. Experimental results indicated that the adsorption was favorable at higher pH and higher temperature. Values of DeltaG degrees ranging from -4.64 to -5.13 kcal mol(-1) for sewage sludge ash and from -4.97 to -5.53 kcal mol(-1) for pomace ash suggest that the adsorption reaction is a physical process enhanced by the electrostatic effect. The values of DeltaH degrees and DeltaS degrees are, respectively, 4.27 kcal mol(-1) and 30.6 cal K(-1)mol(-1) for sewage sludge ash and 4.33 kcal mol(-1) and 31.3 cal K(-1)mol(-1) for pomace ash. The mechanisms of copper removal by these materials included adsorption and precipitation. The sewage sludge and pomace ashes are shown to be effective adsorbents for this metal.     

Disposal of domestic sludge and sludge ash on volcanic soils

Column leaching experiments were conducted to test the ability of Chilean volcanic soils in retaining the mineral constituents and metals in sewage sludge and sludge ash that were incorporated into the soils. Small or negligible amounts of the total content of Pb, Fe, Cr, Mn, Cd, and Zn (0 to <2%), and more significant amounts of mineral constituents such as Na (7-9%), Ca (7-13%), PO4 (4-10%), and SO4 (39-46%) in the sludge and sludge ash were readily soluble. When they were incorporated on the surface layer of the soils and leached with 12 pore volumes of water over a 3 month period of time, less than 0.1% of the total amount of heavy metals and PO4 in the sludge and sludge ash were collected in the drainage water. Cation exchange selectivity, specific anion adsorption and solubility are the processes that cause the reduction of leaching. The volcanic soils were capable of retaining the mineral constituents, P, and metals in applied sewage sludge and sludge ash and gradually released them as nutrients for plant growth.     

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.     

污水厂脱水污泥制吸附剂及脱除H2S效能研究

采用热解炭化法制备了一系列污泥吸附剂,优化制备工艺,利用扫描电镜(SEM)、比表面积和孔径分析等技术对污泥吸附剂的结构进行了表征,并研究了脱除H2S效能。结果表明,活化温度、活化时间和固液比等因素均对污泥吸附剂的碘吸附值产生影响。当活化温度为550℃、活化时间为2.0h、固液比为1∶2时所制备材料(SA)的碘吸附值最高,为493.12mg/g;制备的SA具有较好的脱除H2S效能,能满足精脱硫的要求,当空速为4600h-1时,SA的除臭时间可达48min;此外SA中含有的多种金属元素,平均孔径为3.4nm,这些性质均有利于H2S的吸附脱除。     

Study of Cu(II) biosorption by dried activated sludge: effect of physico-chemical environment and kinetics study

Biosorption is a recent technology used to remove heavy metal ions from aqueous solutions. The biosorption of copper ions from aqueous solution by dried activated sludge was investigated in batch systems. Effect of solution pH, initial metal concentration and particle size range were determined. The suitable pH and temperature for studied conditions were determined as 4.0 and 20 °C, respectively. The theoretical max biosorption capacity of activated sludge was 294 mg g⁻¹ at 20 °C for <0.063 mm particle size. The equilibrium data fitted very well to both Langmuir and Freundlich isotherm models. The pseudo first and second-order kinetic models were used to describe the kinetic data. The experimental data fitted to second-order kinetic model. The particle size and initial metal concentration were effected the biosorption capacity of dried activated sludge. An increase in the initial metal concentration increases of biosorption capacity, which also increases with decreasing particle size. Dried activated sludge has different functional groups according to the FT-IR results.     

A research on sintering characteristics and mechanisms of dried sewage sludge

This study investigates the sintering behavior of dried sewage sludge and the related sintering mechanisms, considering sintering temperature and sintering time. Experimental results indicate that the characteristics are primarily influenced by sintering temperature. When the sintering temperature is increased from 1020 to 1050 °C, the specimens’ compressive strength and bulk density increase significantly, while water absorption decreases obviously, indicating an improvement of densification due to sintering. However, the compressive strength cannot meet the requirement for traditional ceramic products due to the release of organic matters and the formation of big pores in the products. Phosphorus in sewage sludge initially takes reactions with the formation of calcium magnesium phosphate and aluminum phosphate during sintering, which are helpful for enhancing the compressive strength. So, some materials with high contents of Al could be used to enhance the compressive strength of products. Heavy metals are fixed primarily inside the sintered specimens, with the As, Pb, Cd, Cr, Ni, Cu, Zn concentrations in the leachate found to be in the range of China regulatory requirements. These results reveal the feasibility of recycling dried sewage sludge by sintering as a construction material.     

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.     

The influence of heavy metals on the polymorphs of dicalcium silicate in the belite-rich clinkers produced from electroplating sludge

The purpose of this study is to utilize an electroplating sludge for belite-rich clinker production and to observe the influence of heavy metals on the polymorphs of dicalcium silicate (C₂S). Belite-rich clinkers prepared with 0.5–2% of NiO, ZnO, CuO, and Cr₂O₃ were used to investigate the individual effects of the heavy metals in question. The Reference Intensity Ratio (RIR) method was employed to determine the weight fractions of γ-C₂S and β-C₂S in the clinkers, and their microstructures were examined by the transmission electron microscopy (TEM). The results showed that nickel, zinc, and chromium have positive effects on β-C₂S stabilization (Cr³⁺ > Ni²⁺ > Zn²⁺), whereas copper has a negative effect. The addition of up to 10% electroplating sludge did not have any negative influence on the formation of C₂S. It was observed that γ-C₂S decreased while β-C₂S increased with a rise in the addition of the electroplating sludge. Moreover, nickel and chromium mainly contributed to stabilizing β-C₂S in the belite-rich clinkers produced from the electroplating sludge.     

An investigation of heavy metal biosorption in relation to C/N ratio of activated sludge

The effect of C/N ratio of activated sludge on heavy metal biosorption was investigated. Three sets of semi-continuous reactors with different feed C/N ratios (9, 21 and 43 mg COD/mg TKN) were set up. Sorption equilibrium tests have indicated that the biosorptive capacity of activated sludge was highly dependent on metal species and the C/N ratio. The increase in C/N ratio resulted in an increase in the Cd(II) sorption capacity of activated sludge whereas it decreased the Cu(II) sorption capacity. As for Zn(II), a different behavior was observed such that, the highest and lowest capacities have occurred at C/N ratio of 21 and 43, respectively. For Ni(II) biosorption, isotherm tests produced greatly scattered data; so, it was not possible to obtain any plausible result to indicate the relationship between maximum adsorptive capacity and C/N ratio. The accompanying release of Ca(II) and Mg(II) ions and also carbohydrates into the solution during biosorption have indicated that ion exchange mechanism was involved however, was not the only mechanism during the sorption process.     

Effect of distillery sludge on seed germination and growth parameters of green gram (Phaseolus mungo L.)

Experiments were carried out to study the effect of distillery sludge amendments with garden soil (10, 20, 40, 60, 80 and 100%) on seed germination and growth parameters of Phaseolus mungo L. Germination percentage and index values decreased with rise in sludge concentration. Soil amended with 10% (w/w) sludge showed favorable growth while >10% was inhibitory for plant growth. Soil amended with 10% (w/w) distillery sludge induced the growth in root length, shoot length, number of leaves, biomass, photosynthetic pigment, protein and starch while 20% (w/w) sludge amended soil had variable effects on the root, shoot, leaves and nodules of P. mungo L. At concentrations (>40%) reduced all the growth parameters, viz., root length, shoot length, number of leaves, biomass, photosynthetic pigment, protein and starch of P. mungo. Malondialdehyde (MDA) product of lipid peroxidation was also enhanced in both root and leaves of sludge amended soil grown P. mungo at all the sludge amendments and exposure periods. A coordinated increase in cysteine, non-protein thiol and ascorbic acid antioxidants was up to 40 days of growth. After this period a decrease was observed. The N, P, K and Mg accumulation followed the order shoot>leaf>root. Calcium accumulation was highest in the upper part of the plants (including shoot and leaves). Furthermore, heavy metals content were also increased in different parts of P. mungo grown on increasing concentration of sludge amended garden soil with time. Zinc and copper accumulation was maximum versus other heavy metals. Based on these studies, sludge having concentrations < or =10% (w/w) can be applied as a fertilizer.