Thermodynamic behaviors of Cu in interaction with chlorine, sulfur, phosphorus and minerals during sewage sludge co-incineration

Thermodynamic equilibrium calculations were performed to reveal effects of interactions among Cl, S, P and other minerals on Cu migration. Our results showed that HCl（g）, SO2（g） and （P2O5）2（g） were released from the sewage sludge co-incineration. Cl was found to weaken adsorption of Cu by Al2O3, CaO and Fe2O3, while S de- layed reactions of Fe2O3 and Al2O3 with Cu, with P having no effect on reactions between the minerals and Cu. Among the coupled systems ofCl, S and P, the co-existences of Cl and S, and Cl, S and P were determined to inhibit Cu volatilization, and the co-existence of Cl and P had an enhancing effect Cu migration was affected only by S in the S and P system. With the SiO2, CaO and Al2O3 system, both Cl alone and Cl and P led to failed reactions be- tween the minerals and Cu. In the systems of S, S and Cl, S and P, and S, Cl and P, the migration behavior of Cu was mainly affected by S at low temperatures and by Cl at high temperatures, whereas P had no effect on Cu mi- gration during the entire nrocess.

Co-pyrolysis of Sewage Sludge with Paint Sludge: Kinetics and Thermodynamic Analysis via Iso-conversional Methods

This study explored the synergistic interaction of sewage sludge(SS)and automotive paint sludge(PS)during co-pyrolysis for the optimized treatment of sewage sludge in cement kiln systems,utilizing thermogravimetric analysis(TGA)and thermogravimetric-mass spectrometry(TGA-MS).The result reveals the coexisting synergistic and antagonistic effects in the co-pyrolysis of SS/PS.The synergistic effect arises from hydrogen free radicals in SS and catalytic components in PS,while the main source of the antagonistic effect is that,during the mechanical mixing process,the SS/PS is converted from the particulate form into a dough-like rubbery which contributes to the film-forming effect,hindering the volatilization of volatile components.SS/PS co-pyrolysis reduces the yielding of tar production while increasing coke and gas.This study will provide some in-depth insights into the co-pyrolysis of SS/PS,and offer theoretical support for the subsequent research on the collaborative disposal processes in cement kilns.

Co-pyrolysis of Sewage Sludge with Distillation Residue: Kinetics Analysis via Iso-conversional Methods

This study explored the synergistic interaction of sewage sludge(SS)and distillation residue(DR)during co-pyrolysis for the optimized treatment of sewage sludge in cement kiln systems,utilizing thermogravimetric analysis(TGA)and thermogravimetric analysis with mass spectrometry(TGA-MS).The results reveal the coexisting synergistic and antagonistic effects in the co-pyrolysis of SS/DR.The synergistic effect arises from hydrogen free radicals in SS and catalytic components in ash fractions,while the antagonistic effect is mainly due to the melting of DR on the surface of SS particles during pyrolysis and the reaction of SS ash with alkali metals to form inert substances.SS/DR co-pyrolysis reduces the yielding of coke and gas while increasing tar production.This study will promote the reduction,recycling,and harmless treatment of hazardous solid waste.

Total concentrations and different fractions of heavy metals in sewage sludge from Guangzhou, China

Dewatered municipal sludge samples were collected from five municipal wastewater treatment plants （WWTPs） and one industrial WWTP in Guangzhou, China. A number of agricultural parameters and total metal concentrations in the sludge were determined. Metal speciation was also studied. The results showed that sewage sludge had high organic carbon, and was rich in such nutrients as N and P. The concentrations of Mn, Zn, and Cu were the highest, followed by Ni, Pb, and Cr, Cd had the lowest concentration. In addition, the concentrations of the aforementioned heavy metals in the sludge samples were higher than those recorded in the background data for crop soils. With the exception of Cu and Cd from site S1, and Ni from sites S1, $2, and $5, all other metal concentrations conformed to permissible levels prescribed by the national application standard of acid soil in China （GB 18918--2002）. The results of the BCR sequential extraction showed that the concentrations of Mn and Zn were predominant in acid-soluble/exchangeable and reducible fractions. Cu was principally distributed in oxidizable and residual fractions, whereas Cr was present in oxidizable and residual fractions, Pb was found in the state of residual fractions, and the distribution of Ni and Cd did not show significant characteristics.

Analysis of bacterial community structures in two sewage treatment plants with different sludge properties and treatment performance by nested PCR-DGGE method

The bacterial community structures in two sewage treatment plants with different processes and performance were investigated by denaturing gradient gel electrophoresis （DGGE） of nested polymerase chain reaction （nested PCR） amplified 16S rRNA gene fragments with group-specific primers. Samples of raw sewage and treated effluents were amplified using the whole-cell PCR method, and the activated sludge samples were amplified using the extracted genomic DNA before the PCR products were loaded on the same DGGE gel for bacterial community analysis. Ammonia-oxidizing bacterial and actinomycetic community analysis were also carried out to investigate the relationship between specific population structures and system or sludge performance. The two plants demonstrated a similarity in bacterial community structures of raw sewage and activated sludge, but they had different effluent populations. Many dominant bacterial populations of raw sewage did not appear in the activated sludge samples, suggesting that the dominant bacterial populations in raw sewage might not play an important role during wastewater treatment. Although the two plants had different sludge properties in terms of settleability and foam forming ability, they demonstrated similar actinomycetic community structures. For activated sludge with bad settling performance, the treated water presented a similar DGGE pattern with that of activated sludge, indicating the nonselective washout of bacteria from the system. The plant with better ammonium removal efficiency showed higher ammonia-oxidizing bacteria species richness. Analysis of sequencing results showed that the major populations in raw sewage were uncultured bacterium, while in activated sludge the predominant populations were beta proteobacteria.

Effect of four crop straws on transformation of organic matter during sewage sludge composting

A 45-d laboratory experiment was conducted to compare the effect of four crop straws on the transformations of organic matter （OM） during composting of sewage sludge. The four crop straws included rape straw, wheat straw, maize straw and rice straw. The following parameters such as temperature, OM, humic-like substances （HS）, fulvic-like acids （FA） and humic-like acids （HA） were determined. The degradation of OM and the formation of HS and HA could be described well by the first-order kinetic model, while the FA content fluctuated during composting. The maximal degradation rates of OM in the compost piles added with rape straw, wheat straw, maize straw and rice straw were 34.7, 46.9, 54.7 and 52.8%, respectively, and the final contents of HS were 118, 128, 141 and 134 g kg-1, respectively, while the humification indices were higher in the compost piles added with maize straw and wheat straw than in those with rice straw and rape straw. The results indicate that a higher hemicellulose content and a lower C/N ratio in crop straw can result in a higher rate of OM degradation and higher contents of HS, while a higher content of lignin can lead to a higher polymerization degree of humic substances in compost piles. The final compost piles added with maize straw has the highest contents of OM, total nitrogen and humus substance as well as the highest values of polymerization degree, while compost piles with rape straw have the highest potassium content and those with rice straw have the highest pH values.

Leaching of phosphorus from incinerated sewage sludge ash by means of acid extraction followed by adsorption on orange waste gel

Ashes from sewage sludge incineration have a high phosphorus content, approximately 8% （W/W）, which indicates a potential resource of the limiting nutrient. Incineration of sewage sludge with subsequent recovery of phosphorus is a relatively new sludge treatment technique. In this article, the leaching of phosphorus by using sulfuric acid as well as hydrochloric acid by means of several batch experiments was presented. At the same time a selective recovery of phosphorus by adsorption was also discussed. The effects of acid concentration, temperature and time on extraction were studied. The phosphorus leaching increased with the increase in acid concentration and temperature. Kinetic studies showed that the complete leaching of phosphorus took place in less than 4 h. Selective adsorption of phosphorus by using orange waste gel provided a hint for recovery of this natural resource, which eventually could meet the ever-increasing requirement for phosphorus. The overall results indicated that the incinerated sewage sludge ash can be treated with acid to efficiently recover phosphorus and thus can be considered a potentially renewable source of phosphorus.

Plants grown on sewage sludge in South China and its relevance to sludge stabilization and metal removal

The production of sewage sludge in China has been increasing sharply in order to treat 40% of the municipal sewage in 2005 as planned by central government. The main sludge disposal method is landfill owing to heavy metal contamination, but it presents an attractive potential for agricultural land application. Experiments were carried out to study the simultaneous metal removal and sludge stabilization by plants. The sludge samples were collected from Datansha Wastewater Treatment Plant of Guangzhou, it contained excessive Cu and Zn compared with the Chinese National Standard for Agricultural Use of Sewage Sludge. Plants growing on sludge beds were investigated to follow their growth and metal uptake. 30 sludge plants were identified during 1 year's observation. A Zn high accumulating and high growth rate plant (Alocasia macrorrhiza) was selected and grown on sludge beds in plots. The water, organic matter, heavy metals and nutrients contents, the E. coli number and the cress seed germination index were monitored for the sludge samples collected monthly. The plant growth parameters and its heavy metals contents were also determined. The sewage sludge treated by plants could be stabilized at about 5 months, the E. coli number was significantly decreased and the cress seed germination index attained 100%. Crop on sludge could ameliorate the sludge drying. The experiments are continuing to find out the appropriate plant combination for simultaneous sludge stabilization and metal removal for an acceptable period. Comparisons between the proposed processes and other methods for treating produced sludge such as composting, chemical and bacterial leaching were discussed.

Characteristics of sewage sludge and distribution of heavy metal in plants with amendment of sewage sludge

In order to better understand land application of sewage sludge, the characterization of heavy metals and organic pollutants were investigated in three different sewage sludges in Shanghai City, China. It was found that the total concentrations of Cd in all of sewage sludge and total concentrations of Zn in Jinshan sewage sludge, as well as those ofZn, Cu, and Ni in Taopu sludge are higher than Chinese regulation limit of pollutants for sludge to be used in agriculture. Leachability of rig in all of studied samples and that of Cd in Taopu sewage sludge exceed the limit values of waste solid extraction standard in China legislation. Based on the characteristics for three kinds of sewage sludge, a pot experiment was conducted to investigate the effect of soil amended with Quyang sewage sludge on the accumulation of heavy metalo.by Begonia semperfloreas-hybr; Ophiopogon japonicas （L.F.） Ker-Gaw; Loropetalum chindense-var, rubrum; Dendranthema morifolium; Viola tricolor; A ntirrhinum majas; Buxas radicans Sieb; Viburnum macrocephalum; Osmanthas fragrans Lour; Cinnamomum camphora siebold and Ligustrum lucidum ait. Results showed that 8 species of plant survived in the amended soil, and moreover they flourished as well as those cultivated in the control soil. The heavy metal concentration in plants varied with species, As, Pb, Cd and Cr concentration being the highest in the four herbaceous species studied, particularly in the roots of D. morifolium. These plants, however, did not show accumulator of As, Pb, Cd and Cr. The highest concentration of Ni and Hg was found in the roots ofD. morifolium, followed by the leaves ofB. semperflorens-hybr. Levels of Zn and Cu were much higher in D. morifolium than in the other plant species. D. morifolium accumulated Ni, Hg, Cu and Zn, which may contribute to the decrease of heavy metal contents in the amended soil. Treatment with sewage sludge did not significantly affect the uptake of heavy metals by the L. chindense-var, rubrum, however, it significantly affected the uptake of heavy metals by D. morifolium.

Changes of Cu, Zn, and Cd speciation in sewage sludge during composting

The potential toxicity risks from heavy metals depend on their chemical speciation. The four stages of the Tessier sequential extraction method were employed to investigate changes in heavy metal speciation （Cu, Zn, and Cd） of sewage sludge during forced aeration composting, and then to identify whether the composting process would reduce or enhance their toxicities. Throughout the composting process, the exchangeable, carbonate-bound, Fe-Mn oxide-bound, and organic matter-bound fractions of Cu were converted to the residual Cu fraction. The organic matter-bound Cu fraction greatly contributed to this transformation. Residual Zn fraction was transformed to the Fe-Mn oxide-bound and organic matter-bound fractions after composting. The residual Zn fraction was a major contributor to the organic matter-bound Zn fraction. The availability of Cu and Zn was reduced by composting such that the risk of heavy metal toxicity decreased with prolonged treatment times. Additionally, attention should be paid to the increased availability of Cd in sewage sludge after composting treatment.

Removal of heavy metals from sewage sludge by low costing chemical method and recycling in agriculture

Experiments were carried out to study the removal of heavy metals from municipal sewage sludge by proper method for land application. The sequential extractions for metal fractionation showed that the non digested sludge from Guangzhou contained Cu and Zn principally bound to carbonate and oxides and the metal sulfides were low. Among H 2SO 4, EDTA and NH 4HCO 3 extractant agents, H 2SO 4 was the most efficient and economic in removing the heavy metals, especially with the addition of the concentrated acid. Plant experiment in pots with Chinese cabbage ( Brassica Chinensis ) showed that the acidified sludges neutralized with alkaline amendments such as phosphate rock could increase significantly the plant yield and decreased the soil and plant contamination by heavy metals originated from sewage sludge.

Changes of Cu, Zn, and Ni chemical speciation in sewage sludge co-composted with sodium sulfide and lime

A batch composting study was performed to evaluate the feasibility of co-composting sewage sludge with sodium sulfide and lime （SSL） mixture （Na2S/CaO= 1：1）, aiming at reducing the availability of heavy metals in the sludge compost. Sewage sludge with sawdust as a bulking agent was amended with SSL at 3% （w/w, dw）, and composted for 15 d in laboratory batch reactors. The four stages of the Tessier sequential extraction method was employed to investigate changes in heavy metal fractions of Cu, Zn, and Ni in sewage sludge composted with SSL. For all the three metals, the mobile fractions, such as, exchangeable and carbonate bound were mainly transformed into low availability fractions （organic matter and sulfide, Fe-Mn oxides bound and residual forms）, and the addition of SSL enhanced this transformation. Therefore, SSL is a suitable material to co-compost with sewage sludge to reduce the availability of heavy metals. According to the cabbage seed germination test, a SSL amendment of ≤3% （w/w, dw） is recommended to co-compost with sewage sludge.

Effects of thermally pretreated temperature on bio-hydrogen production from sewage sludge

Hydrogen can be obtained by anaerobic fermentation of sewage sludge. Therefore, in this paper the effects of thermally pretreated temperatures on hydrogen production from sewage sludge were investigated under different pre-treatment conditions. In the thermal pretreatment, some microbial matters of sludge were converted into soluble matters from insoluble ones. As a result, the suspended solid（SS） and volatile suspended solid（VSS） of sludge decreased and the concentration of soluble COD（SCOD） increased, including soluble carbohydrates and proteins. The experimental results showed that all of those pretreated sludge could produce hydrogen by anaerobic fermentation and the hydrogen yields under the temperatures of 121℃ and 50℃ were 12.23 ml/g VS（most） and 1.17 ml/g VS （least）, respectively. It illuminated that the hydrogen yield of sludge was affected by the thermally pretreated temperatures. Additionally, the endurance of high hydrogen yield depended on the translation of microbial matters and inhibition of methanogens in the sludge. The temperatures of 100℃ and 121℃ （treated time, 30 min） could kill or inhibit completely the methanogens while the others could not. To produce hydrogen and save energy, 100℃ was chosen as the optimal temperature for thermal pretrcatment. The composition changes in liquid phase in the fermentation process were also discussed. The SCOD of sludge increased, which was affected by the pretreatment temperature. The production of volatile fatty acids in the anaerobic fermentation increased with the pretreatment temperature.

Effect of pyrolysis temperature and hold time on the characteristic parameters of adsorbent derived from sewage sludge

According to the Doehlert's matrix method, the adsorbent derived from sewage sludge was prepared through chemical activation under controlling the pyrolysis temperature and hold time. The characteristic parameters including the total yield, adsorption of methylene blue, adsorption of iodine, BET surface area, micro-pore volume are 35%—49%, 16.5—38 mg/g, 285—362 mg/g, 185—359 m2/g, and 0.112—0.224 m3/g, respectively. According to the experimental data, the multi-linear regression method was adopted to fit the relations between the characteristic parameters and influential factors. At final, through optimization method, the optimal adsorbent is obtained when using 62 min as hold time and 1105K as pyrolysis temperature. Under the conditions, the adsorbent was produced and compared the characteristic parameters with model forecast value, the coherence is satisfied.

Extraction of copper from sewage sludge using biodegradable chelant EDDS

[S,S]-Ethylenediaminedisuccinic acid(EDDS),a biodegradable chelant,was used to separate the heavy metals from the sewage sludge based on chemical extraction technology.Under various conditions,the extraction experiments were carried out for the sewage sludge from Shanghai Taopu Municipal Wastewater Plant,China.The influences ofpH and the concentration of EDDS on the extraction efficiency for copper(Cu)were discussed.The results showed that EDDS had higher extraction efficiency for Cu from the sewage sludge ...

Levels and distributions of polychlorinated biphenyls in sewage sludge of urban wastewater treatment plants

Concentrations of polychlorinated biphenyls （PCBs） have been measured in sewage sludge samples from 8 urban wastewater treatment plants in Beijing, China. The PCB congeners were analyzed by isotope dilution high resolution gas chromatography/high resolution mass spectrometry method. The concentration of PCBs ranged from 65.6 to 157 ng/g dry weight （dw）, with a mean value of 101 ng/g dw. The dioxin-like PCB WHO-TEQs （World Health Organization-Toxic Equivalents） of the sludge were lower than 1 pg /g dw. Consequently, all the concentrations of PCBs in sludge samples were below the upper limit for land application according to the Chinese legislation law for agriculture use. The PCB homologue profiles in sludge samples were dominated by tri-CBs and tetra- CBs. Similar distributions have been found in one of the Chinese PCB commercial products. The patterns of dioxin-like and indicator congeners observed in this study were quite similar in all samples. The predominant congener for dioxin-like and indicator PCBs were PCB-118 and PCB-28, respectively, while PCB-126 had the highest TEQ value.

Emission characteristics of dioxins,furans and polycyclic aromatic hydrocarbons during fluidized-bed combustion of sewage sludge

Pre-dried sewage sludge with high sulfur content was combusted in an electrically heated lab-scale fluidized-bed incinerator. The emission characteristics of polychlorinated dibenzo-p-dioxins （PCDDs）, polychlorinated dibenzofurans （PCDFs） and polycyclic aromatic hydrocarbons （PAHs） were studied. Coal and calcium oxide （CaO） were added during the sewage sludge combustion tests to optimize combustion conditions and control SO2 emission. The results indicated that the flue gases emitted during mono-combustion of sewage sludge were characterized by relatively high concentrations of SO2, NOx and organic pollutants, due to the high sulfur, nitrogen, and volatile matter content of sewage sludge. The total 16 USEPA priority PAHs and 2,3,7,8-substituted PCDD/Fs produced from sewage sludge combustion were found to be 106.14 μg/m^3 and 8955.93 pg/m^3 in the flue gas, respectively. In the case of cocombustion with coal （msludge/mcoal =1：1）, the 16 PAHs and 2,3,7,8-substituted PCDD/Fs concentrations were markedly lower than those found during mono-combustion of sewage sludge. During co-combustion, a suppressant effect of CaO on PCDD/Fs formation was observed.

The Hydrochar Characters of Municipal Sewage Sludge Under Different Hydrothermal Temperatures and Durations

Innovative measure is a urgent requirement for managing the huge volume of municipal sewage sludge. The hydrothermal carbonation （HTC） shows some potential advantages for using hydrochar as a soil conditioner. The aim of this work was to investigate the properties of hydrochars, by means of the HTC of municipal sewage sludge under different temperatures （190 and 260~C） and reaction hours （1, 6, 12, 18 and 24 h）. The HTC led to the decreases of N, O and H contents by more than 54.6, 37.9 and 10.0%, respectively, and slight changes of C content. The Py-GC-MS analysis showed that a large proportion of fatty acids, in particular hexadecanoic acid, transferred into alkenes, olefins and aromatic compounds. The 13C-NMR and fourier transform infrared spectra （FTIR） confirmed the transformation and changes in chemical structure in which hydrochar contained lower oxygen-containing organic C of O-alkyl, carboxylic and carbonyl C and aliphaticity, but higher aromatic C and aromaticity. The rich hydrophobic functions induced in high positive charges in the charred sludge. The HTC facilitated the pore structure development, proved by higher specific surface area and specific pore volume, with a maximum of 17.30 and 0.83 cm^3 g^-1, respectively. The availabilities of N, P and K markedly reduced during HTC treatment. The activities of most heavy metals were depressed though they accumulated in the hydrochar. Further work is required to investigate the values and risk of the charred sludge amended to soil.

Accumulation and bioavailability of heavy metals in a soil-wheat/maize system with long-term sewage sludge amendments

A long-term field experiment was carried out with a wheat-maize rotation system to investigate the accumulation and bioavailability of heavy metals in a calcareous soil at different rates of sewage sludge amendment. There are significant linear correlations between the contents of Hg, Zn, Cu, Pb, and Cd in soil and sewage sludge amendment rates. By increasing 1 ton of applied sludge per hectare per year in soil, the contents of Hg, Zn, Cu, Pb, and Cd in soil increased by 6.20, 619, 92.9, 49.2, and 0.500 μg kg–1, respectively. For Hg, sewage sludge could be safely applied to the soil for 18 years at an application rate of 7.5 t ha–1 before content exceeded the soil environmental quality standards in China(1 mg kg–1). The safe application period for Zn is 51 years and is even longer for other heavy metals(112 years for Cu, 224 years for Cd, and 902 years for Pb) at an application rate of 7.5 t ha–1 sewage sludge. The contents of Zn and Ni in wheat grains and Zn, Cu, and Cr in maize grains increased linearly with increasing sewage sludge amendment rates. The contents of Zn, Cr, and Ni in wheat straws and Zn, Cu, and As in maize straws were positively correlated with sewage sludge amendment rates, while the content of Cu in wheat straws and Cr in maize straws showed the opposite trend. The bioconcentration factors of the heavy metals in wheat and maize grains were found to be in the order of Zn>Cu>Cd>Hg>Cr=Ni>Pb>As. Furthermore, the bioconcentration factors of heavy metals in wheat were greater than those in maize, indicating that wheat is more sensitive than maize as an indicator plant. These results will be helpful in developing the critical loads for sewage sludge amendment in calcareous soils.

Effect of substrate concentration on the bioleaching of heavy metals from sewage sludge

The effect of elemental sulfur concentration on bioleaching of Cu, Zn and Pb and loss of fertilizer value from sewage sludge was investigated in flasks by batch experiments. The results showed that the ultimate pH of sludges with 3—5 g/L of sulfur added was about 1.3 and the production of SO 2- 4 had good correlation with the elemental sulfur concentration. The sensitivity of removal efficiency of metals to sulfur concentration was: Pb>Cu>Zn. The sulfur concentration except for 3—5 g/L had significant effect on the solubilization of Cu, Pb and Zn. The highest solubilization efficiency for sludge with 3 g/L of sulfur was 87.86% for Cu, 32.72% for Pb and 92.14% for Zn, which could make the treated sludge easily meet the metal limitations for land application. The sulfur concentration of 3 g/L was enough for the solubilization of all three heavy metals. The influence of sulfur concentration on solubilization of total nitrogen and potassium from sludge was negligible, but that on solublization of total phosphorus was of great importance. The loss of nitrogen, phosphorus and potassium of sludge with 3 g/L of sulfur by bioleaching was 38.2%, 52.1% and 42.8% respectively, and the sludge still remained satisfactory fertilizer value after bioleaching.