Metal remediation from partially composted distillery sludge using composting earthworm Eisenia fetida

Distillery sludge, a sugar industry byproduct, has been recommended widely as a potential soil conditioner, but high concentrations of metals limit its continuous use for field crops. In this study we tested the feasibility of earthworm Eisenia fetida (Savigny) in removing metals (Fe, Cu, Zn, Pb) from sludge through vermitechnology. The transfer of metals during the vermicomposting process was also estimate in terms of total metal contents in vermicomposted sludge and earthworm tissues. The sludge processed by worms showed a significant reduction in concentration of metals: Zn (20.5-43.8%), Fe (23.6-34.0%), Mn (18.0-45.7%) and Cu (29.0-58.1%), at the end. The metal reduction in sludge was directly related to the bioaccumulation of metals in the tissues of composting earthworms. The inoculated earthworms showed a considerable level (dry wt basis) of Zn (103.7-143.3 mg kg(-1)), Fe (87.2-146.5 mg kg(-1)), Mn (83.7-138.6 mg kg(-1)) and Cu (16.8-25.5 mg kg(-1)) in their tissues. A higher range of bioconcentration factors (BCFs) for different metals studied further suggest the candidature of earthworm to be used effectively for removal of metals form industrial sludges. The obtained vermicomposts form different vermireactors were rich in nutrients. The feasibility of earthworms to mitigate the metal toxicity and to enhance the nutrient profile in sludge might be useful in sustainable land restoration practices at low-input basis. The ranges of metals in end product were within the standards recommended by different agencies.     

Environmentally safe sewage sludge disposal: the impact of liming on the behaviour of Cd, Cr, Cu, Fe, Mn, Ni, Pb, and Zn

Dewatered sewage sludge containing relatively high total concentrations of Cr (945 micrograms ml-1), Cu (523 micrograms ml-1), Ni (1186 micrograms ml-1) and Zn (2950 micrograms ml-1) was treated with quicklime and sawdust for sludge disinfection and post-stabilisation. The mobility of the heavy metals in the sludge samples was assessed by applying a modified five-step Tessier sequential extraction procedure. Water was added as a first step for estimation of the proportion of the easily soluble metal fractions. To check the precision of the analytical work the concentrations of heavy metals in steps 1-6 of the extraction procedure were summed and compared to the total metal concentrations. The mass balance agreed within +/- 3% for Cd, Cu, Cr, and Zn and within +/- 5% for Ni, Pb, Fe and Mn. Data from the partitioning study indicate that in the lime-treated sludge at a pH of 12 the mobility of Cu and Ni notably increased with the solubilisation of these metals from their organic and/or carbonate and Fe and Mn oxide and hydroxide fractions, respectively. Liming slightly decreased the proportion of other heavy metals in the easily soluble fractions while its impact on the partitioning between other sludge phases was almost insignificant. Due to the increased solubility of Ni and Cu as well as potential Cr oxidation at high pH, liming cannot be recommended for sludge disinfection. Addition of sawdust did not change the heavy metal partitioning.     

Impact of ultrasonic treatment on dewaterability of sludge during Fenton oxidation

Fenton oxidation was compared with Fenton oxidation coupled with ultrasonication (Fenton?+?US) for sludge dewatering. Different Fenton reagent (H₂O₂, Fe²⁺) concentrations, pH, and reaction times were studied in different systems on the basis of the specific resistance to filtration (SRF) and capillary suction time (CST). It was found that Fenton?+?US can significantly reduce Fe²⁺ and H₂O₂ dosages and reaction times. After ultrasonication of the system at pH 3, with an ultrasonic frequency of 25 kHz and a sound energy density of 100 W/L, the Fe²⁺, H₂O₂ dosage, and reaction time were reduced by 66.7, 75.0, and 75.0 %, respectively, when compared with Fenton oxidation at the same dewaterability of sludge. The microstructure of sludge and hydroxyl radical (·OH) density in Fenton oxidation and Fenton?+?US was further examined. Fenton?+?US produced more?·?OH in a sludge system than did individual Fenton oxidation. The concentration of?·?OH in Fenton?+?US fell from 79.2 to 6 mg/L over 3.5 h, while the concentration of?·?OH in Fenton oxidation fell from 59.6 to 1 mg/L over 2 h, thus destroying the microstructure of sludge more effectively. Sludge treated using Fenton?+?US for 30 min showed a much thinner and looser microstructure.     

Preconcentration of Zn2+ and Cu2+ ions from food and vegetable samples using modified activated carbon

In this work, two N/S-containing chelating agents 2-(4-methoxybenzylideneamino)thiophenol (2-4-MBAT) and 2-(4-chlorobenzylideneamino) benzenethiol (2-4-CBABT) were synthesized as new sorbents and were used for preconcentration of Zn(2+) and Cu(2+) ions in food and vegetable samples. In the proposed procedure, the trace amount of Zn(2+) and Cu(2+) ions from 250?mL of sample solution at pH?=?5.0 was preconcentrated by 1?g of activated carbon (AC) loaded with 15?mg of 2-4-MBAT and 2-4-CBABT separately. The breakthrough volumes (maximum sample volume that their metal ions quantitatively can be enriched) for solid-phase extraction (SPE) procedure based on the AC modified with 2-4-MBAT and 2-4-CBABT were 800 and 750?mL, respectively. The sorbed Zn(2+) and Cu(2+) ions were efficiently eluted by 8?mL of 4?mol?L(-1) HNO(3) and preconcentration factor of 112.5 and 93.7 and experimental enhancement factor of 30 and 35 ions were obtained for Zn(2+) and Cu(2+), respectively. The application of this enrichment procedure allowed the extraction of trace metal ions with recoveries exceeding of 90%.     

Environmental risk assessment of heavy metal extractability in a biosludge from the biological wastewater treatment plant of a pulp and paper mill

A five-stage sequential extraction procedure was used to fractionate heavy metals (Cd, Cu, Pb, Cr, Zn, Fe, Mn, Ni, Co, As, V and Ba) in a biosludge from the biological wastewater treatment plant of Stora Enso Oyj Veitsiluoto Mills at Kemi, Northern Finland, into the following fractions: (1) water-soluble fraction, (2) exchangeable fraction, (3) easily reduced fraction, (4) oxidizable fraction, and (5) residual fraction. The biosludge investigated in this study is a combination of sludge from the primary and secondary clarifiers at the biological wastewater treatment plant. Extraction stages (2)–(4) follow the protocol proposed by the Measurements and Testing Program (formerly BCR Programme) of the European Commission, which is based on acetic acid extraction (stage 2), hydroxylamine hydrochloride extraction (stage 3), and hydrogen peroxide digestion following the ammonium acetate extraction (stage 4). The residual fraction (stage 5) was based on digestion of the residue from stage 4 in a mixture of HF + HNO₃ + HCl. Although metals were extractable in all fractions, the highest concentrations of most of the metals occurred in the residual fraction. From the environmental point of view, it was notable that the total heavy metal concentrations in the biosludge did not exceed the maximal allowable heavy metal concentrations for sewage sludge used in agriculture, set on the basis of environmental protection of soil by European Union Directive 86/278/EEC, and by the Finnish legislation. The Ca (98.6 g kg⁻¹; dry weight) and Mg (2.2 g kg⁻¹; dry weight) concentrations in the biosludge were 62 and 11 times higher than the typical values of 1.6 and of 0.2 g kg⁻¹ (dry weight), respectively, in arable land in Central Finland. The biosludge had a slightly alkaline pH (∼8.30), a high loss-on-ignition value (∼78%) and a liming effect of 10.3% expressed as Ca equivalents (dry weight). This indicates its potential as a soil conditioner and improvement agent, as well as a pH buffer.     

Assessment of aluminum bioavailability in alum sludge for agricultural utilization

Inorganic aluminum ions, [Al(H₂O)₆]³⁺, [Al(OH)(H₂O)₅]²⁺, and [Al(OH)₂(H₂O)₄]⁺, are toxic to a number of crops. The aim of this study was to estimate the danger of soil contamination of bioavailable aluminum and heavy metals forms because of alum sludge which was a by-product of water, and wastewater treatment technology using aluminum coagulant is introduced into the soil. Aluminum and selected heavy metal fractionation was carried out in the post-coagulation sludge collected at a water treatment plant (where aluminum was used as a coagulant), fermented sewage sludge at a municipal wastewater treatment plant (which did not apply aluminum coagulant), and soil from water treatment plant as well as the mixtures of sludge and soil. It has been found that post-coagulation sludge used as natural fertilizer is a secondary source of bioavailable aluminum, especially when aluminum coagulants are used during water and wastewater treatment. The evaluation of applicability of the sludge to very weak acidic and acidic agricultural soils was carried out. The authors shall debate the question whether, in this case, the Regulation of EU and Polish Government on sewage sludge should also take the bioavailable aluminum into account and add to the list of the elements whose allowable contents are limited.     

Comparison of TCPP concentrations in sludge and wastewater in a typical German sewage treatment plant-comparison of sewage sludge from 20 plants

Tris(chloro-isopropyl)phosphate (TCPP) was identified by GC-MS by comparing mass spectra and retention times to original standards. The concentrations in wastewater of a sewage treatment plant's influent and effluent were analysed (520 ng l(-1) and 380 ng l(-1), respectively (mean values). The concentrations of TCPP in the wastewater inflow exhibited a high variability. The elimination of this compound in the sewage treatment plant also exhibits a high variability but is low. Additionally the concentrations in sewage sludge of the same plant were determined (mean value 5100 ng g(-1) dry weight; 1700 ng g(-1) wet weight, respectively). For a comparison sludge samples from twenty other plants were analysed. In these samples concentrations ranging from 1000-20000 ng g(-1)(dry weight) were determined. Thus sorption to sludge does occur to some extent.     

Assessing the feasibility of wastewater recycling and treatment efficiency of wastewater treatment units

Wastewater reuse can significantly reduce environmental pollution and save the water sources. The study selected Cheng-Ching Lake water treatment plant in southern Taiwan to discuss the feasibility of wastewater recycling and treatment efficiency of wastewater treatment units. The treatment units of this plant include wastewater basin, sedimentation basin, sludge thickener and sludge dewatering facility. In this study, the treatment efficiency of SS and turbidity were 48.35–99.68% and 24.15–99.36%, respectively, showing the significant removal efficiency of the wastewater process. However, the removal efficiencies of NH₃–N, total organic carbon (TOC) and chemical oxygen demand (COD) are limited by wastewater treatment processes. Because NH₃–N, TOC and COD of the mixing supernatant and raw water are regulated raw water quality standards, supernatant reuse is feasible and workable during wastewater processes at this plant. Overall, analytical results indicated that supernatant reuse is feasible.     

Chemical oxidation of C. I. Reactive Red 2 using Fenton-like reactions

A detailed investigation on the kinetics of the oxidative degradation of a reactive dye, C. I. Reactive Red 2 by hydroxyl radicals generated by H202 and Fe2+ has been carried out in aqueous acidic media. Effects of different parameters like initial concentration of dye, H2O2, Fe2+, pH of the solution, reaction temperature and added electrolytes on the oxidation process have been studied. The results indicate that 1.63 x 10(-4) mol dm(-3) dye can be most effectively degraded at a dye: Fe2+: H2O2 molar ratio of 1:0.22: 8.13 at pH approximately 2.7 and at 299 K. The addition of excess 2-propanol or t-butyl alcohol, well known scavengers of hydroxyl radicals, almost stopped the degradation of the dye indicating the absence of any possible reductive pathways in the degradation. The results may be useful for designing the treatment systems of wastewater containing various reactive dyes.     

Heavy metal concentration and speciation of seven representative municipal sludges from wastewater treatment plants in Northeast China

The analysis of heavy metals is very important for assessing the feasibility of the agricultural utilization for the municipal sludge. In this paper, a four-step sequential extraction method was applied to extract heavy metals (Cu, Zn, Mn, Cr, and Ni) in municipal sludges from seven individual wastewater treatment plants located in Jilin and Heilongjiang Province, China, for estimating the mobility and bioavailability of the metal ions in the agricultural application. The total concentrations of heavy metals and their chemical fractions after the sequential extraction were determined. Principal component analysis (PCA) was applied to analyze the relations of heavy metals fractions in the municipal sludges. Experimental results indicated that the total concentrations of Cu, Zn, Cr, and Ni in all sludge samples were below the threshold values set out by the Chinese legislation (GB18918-2002). Specially, Zn had a high bioavailability and mobility, Cu and Cr had potential bioavailability, while Mn mainly existed in the residual fraction of municipal sludge. On the other hand, Ni had different mobility in different municipal sludge. PCA results were confirmed by the environmental behavior of heavy metals.     

Solid phase extraction of Cu(II), Ni(II), Pb(II), Cd(II) and Mn(II) ions with 1-(2-thiazolylazo)-2-naphthol loaded Amberlite XAD-1180

A new method for separation and preconcentration of trace amounts of Cu(II), Ni(II), Pb(II), Cd(II) and Mn(II) ions in various matrices was proposed. The method is based on the adsorption and chelation of the metal ions on a column containing Amberlite XAD-1180 resin impregnated with 1-(2-thiazolylazo)-2-naphthol (TAN) reagent prior to their determination by flame atomic absorption spectrometry (FAAS). The effect of pH, type, concentration and volume of eluent, sample volume, flow rates of sample and elution solutions, and interfering ions have been investigated. The optimum pH for simultaneous retention of all the metal ions was 9. Eluent for quantitative elution was 20 ml of 2 mol l(-1) HNO(3). The optimum sample and eluent flow rates were found as 4 ml min(-1), and also sample volume was 500 ml, except for Mn (87% recovery). The sorption capacity of the resin was found to be 0.77, 0.41, 0.57, and 0.30 mg g(-1) for Cu(II), Ni(II), Cd(II), and Mn(II), respectively. The preconcentration factor of the method was 200 for Cu(II), 150 for Pb(II), 100 for Cd(II) and Ni(II), and 50 for Mn(II). The recovery values for all of the metal ions were > or = 95% and relative standard deviations (RSDs) were < or = 5.1%. The detection limit values were in the range of 0.03 and 1.19 microg l(-1). The accuracy of the method was confirmed by analysing the certified reference materials (TMDA 54.4 fortified lake water and GBW 07605 tea samples) and the recovery studies. This procedure was applied to the determination of Cu(II), Ni(II), Pb(II), Cd(II) and Mn(II) in waste water and lake water samples.     

Effects of multi-metal toxicity on the performance of sewage treatment system during the festival of colors (Holi) in India

The present study investigated the effects of heavy metals (Ni, Zn, Cd, Cu, and Pb) toxicity on the performance of 18 MLD activated sludge process-based sewage treatment plant (STP) during celebration of Holi (festival of colors in India). The composite sampling (n?=?32) was carried out during the entire study period. The findings show a significant decrease in chemical oxygen demand removal efficiency (20%) of activated sludge system, after receiving the heavy metals laden wastewater. A significant reduction of 40% and 60% were observed in MLVSS/MLSS ratio and specific oxygen uptake rate, which eventually led to a substantial decrease in biomass growth yield (from 0.54 to 0.17). The toxic effect of metals ions was also observed on protozoan population. Out of the 12 mixed liquor species recorded, only two ciliates species of Vorticella and Epistylis exhibited the greater tolerance against heavy metals toxicity. Furthermore, activated sludge shows the highest metal adsorption affinity for Cu, followed by Zn, Pb, Ni, and Cd (Cu?>?Zn?>?Pb?>?Ni?>?Cd). Finally, this study proves the robustness of activated sludge system against the sudden increase in heavy metal toxicity since it recovered the earlier good quality performance within 5?days.     

电镀废水中重金属的回收处理技术

电镀企业产生的漂洗水中含有大量的重金属,处理后生成的电镀重金属污泥属于危废,国家有相关的处置规定,若处置不当,会对环境造成二次污染,并且造成重金属的流失。介绍了利用离子交换法、电解法、膜分离技术、电去离子法等相关方法回收电镀漂洗废水中重金属的国内外的研究进展;从源头抓起,减少了电镀企业重金属元素的排放量,同时对废水的合理回用提供一些可行性方案。     

Remediation of drinking water contaminated with arsenic by the electro-removal process using different metal electrodes

The purification of water by the electro-removal process using different metal electrodes is widely used in different spheres of science and industry. The comparative characteristics under galvanostatic conditions of zinc (Zn), brass (Cu-Zn), copper (Cu) and iron (Fe) anodes for arsenic (As) removal from water by the electro-removal process in laboratory scale experiments were determined at current densities of 1.5, 3 and 12 mA cm(-2) for 60 min, from a solution containing different concentrations of As(v) (from 70 to 130 microg L(-1)). The results at these different current densities indicated that rapid arsenic removal was achieved at higher current densities (12 mA cm(-2)), with the chemical precipitation of arsenate complexes. The removal of As was relatively efficient, with the following tendency (at 1.5 mA cm(-2)): Fe (>93%) congruent with Zn (>93%) > Cu-Zn (>73%) >Cu (>67%), these efficiencies were relatively independent of the removal rate for all the initial arsenic concentrations investigated. This behaviour is attributed to the electrochemical intrinsic properties of the most active metals, and to the chemical precipitation reactions following the electrochemical process, iron being the most attractive metal for arsenic removal for practical applications.     

Predicting bioavailability of metals from sludge-amended soils

We attempted to develop a protocol for fixing the maximum permissible limit of sludge in agricultural lands based on transfer of metals from sludge-amended soils to human food chain. For this purpose, spinach was grown as a test crop on acid and alkaline soils with graded doses of sludge (0, 1.12, 2.24, 4.48, 8.96, 17.9, 35.8, 71.6, 142 and 285 g kg^?1 of soil) in a pot experiment. Biomass yield of spinach was increased due to sludge application in both acid and alkaline soils. Among the chemical extractants, EDTA extracted the highest amount of metals from sludge-amended soil followed by diethylenetriaminepentaacetic acid (DTPA) and CaCl₂. Elevated levels of Zn, Cu, Fe, Mn, Ni, Cd and Pb in spinach were observed due to sludge application over control. Application of sludge was more effective in increasing metal content in spinach grown on acid soil than alkaline soil. Solubility-free ion activity model as a function of pH, organic carbon and extractable metal was far more effective in predicting metal uptake by spinach grown on sludge-amended soils as compared to that of chemical extractants. Risk in terms of hazard quotient (HQ) for intake of metals through consumption of spinach by humans grown on sludge-treated soils was computed for different metals separately. In a 90-day pot experiment, safe rates of sludge application were worked out as 4.48 and 71.6 g kg^?1 for acid and alkaline soils, respectively.     

Spectrophotometric determination of persulfate by oxidative decolorization of azo dyes for wastewater treatment

Persulfate can efficiently decolorize azo dyes through oxidizing these compounds, which enabled us to develop a method of rapid spectrophotometric determination of persulfate for monitoring the wastewater treatment on the basis of the oxidation decolorization of azo dyes. Four azo dyes with different molecular structures were investigated as probes, and the influences of operation parameters including reaction time, solution pH, initial dye concentration, and initial concentration of activator Fe(2+) were checked on the determination of persulfate. Under optimum conditions, the decolorization degree of the dyes responded linearly with persulfate concentration for all the four azo dyes, and the linear range and detection limit were found to be 2.0-150 μmol L(-1) and 0.62 μmol L(-1) for rhodamine B, 2.0-100 μmol L(-1) and 0.42 μmol L(-1) for methylene blue, 4.0-150 μmol L(-1) and 0.50 μmol L(-1) for methyl violet, and 20-150 μmol L(-1) and 8.1 μmol L(-1) for orange II. A persulfate treatment of a spiked wastewater sample was satisfactorily monitored with the new method.     

Assessment of current status of zinc in wastewater treatment plants to set effluent standards for protecting aquatic organisms in Japan

New environmental standards for protecting aquatic organisms for zinc (e.g., 0.03 mg/L) in surface waters were set in Japan in 2003. Although wastewater effluent might be one of the major pathways of zinc to public water bodies in Japan, current status of concentration of zinc in wastewater effluent was not clear due to higher detection limits (e.g., 0.5 mg/L) than the level required by the new regulations. This study aims at assessing current status of zinc in wastewater effluent in Japan to revise wastewater effluent standards for protecting aquatic organisms. Survey of zinc in wastewater treatment plants (WWTPs) was carried out in Japan in 2005, setting the detection limits at least 0.01 mg/L. The results of the survey suggested the difficulty to remove zinc (especially dissolved zinc) with conventional activated sludge treatment if concentration of zinc in influent was relatively low. And it was suggested that high concentration of dissolved zinc might be derived from some industries discharging high concentration of zinc. The concentration of zinc in wastewater influent without industrial discharges was about 0.1 mg/L which might be lower than that in wastewater from industries discharging high concentration of zinc. Finally, effluent standards for point sources including WWTPs to public water bodies were set at 2 mg/L in 2006. Based on the results of the survey that it was difficult to remove dissolved zinc discharged from industries at WWTPs, the effluent standards from industries to sewerage were set at the same value of the effluent standards from WWTPs to public water bodies.     

Assessment of Treatment Alternatives for Laboratory COD Wastewater: a Practical Comparison with Emphasis on Cost and Performance

This study focused on investigation of treatment alternativesfor COD wastewater from academic laboratories, using a number oftechnologies including chemical reduction/precipitation, ion exchange and adsorption by chitosan. Results showed that highconcentrations of 375 mg l^-1 chromium, 1,740 mg l^-1mercury and 993 mg l^-1 silver in COD wastewater can be reduced to 2.34 mg l^-1, 3.65 mg l^-1 and 1.89 mg l^-1 respectively, by the chemical reduction/precipitationprocess. Results from ion exchange at a flowrate of 20 ml min^-1 showed breakthrough effluent concentrations obtainedat 0.59 mg l^-1 chromium, 3.92 g l^-1 mercury and 0.65 mg l^-1 silver corresponding to 75.6 l at 63 hr, 40.8 l at 34 hr and 33.6 l at 28 hr respectively. Kinetic and isotherm studies revealed that chitosan can adsorb Cr⁶⁺, Hg²⁺ and Ag⁺ ions most effectively at a flowrate of 20 ml min^-1 and the optimum pH for feed solution is 4. Chitosan column experiments indicated that average effluent concentrations at breakthrough point for chromium, mercury andsilver are 0.76 mg l^-1, 6.04 mg l^-1 and 0.51 mg l^-1 respectively with throughput volumes and retention times of 120 l at 100 hr, 60 l at 50 hr and 48 l at 40 hr. Results of solidification experiments for chemical sludge and residual chitosan based on compressive strength and metal leachabilitytests showed, that the acceptable ranges of the solidificationparameters were: sludge/cement = 0.1–1.0 (weight/weight), water/cement = 0.5–0.6 (weight/weight) and sand/cement = 0.5–3.0 (weight/weight). Operating cost per litre of COD wastewater treated, based on the current prices in Thailand wasfound to be Baht 19.95 for the chemical reduction/precipitationprocess, Baht 96.35 for ion exchange treatment and Baht 18.29 forchitosan adsorption.     

Characteristic occurrence patterns of micropollutants and their removal efficiencies in industrial wastewater treatment plants

The concentrations and removal efficiencies of various kinds of micropollutants were investigated and the relationships between the input sources of industrial wastewater and occurrence patterns of each micropollutant were identified at nine on-site industrial wastewater treatment plants (WWTPs). The distribution pattern of each compound varied according to the WWTP type and several micropollutants were significantly related with specific industries: chlorinated phenols (ClPhs) with paper and metal industries, polycyclic aromatic hydrocarbons (PAHs) with petrogenic- and pyrogenic-related industries, polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) with the paper industry, and chlorinated benzenes (ClBzs) with dye-related industries. The activated sludge (AS) process was very efficient in the removal of ClPhs and PAHs, and the filtration process in the removal of PCDD/Fs and 1,4-dioxane. Generally, the removal efficiencies of each micropollutant varied according to the WWTP type.     

Ionic and heavy metal composition of respirable particulate in Madurai, India

Airborne particulate matter (PM₁₀) was collected for a period of 1 year at six locations in Madurai city, India. The chemical analyses on PM₁₀ samples were carried out for the estimation of heavy metals and ions using atomic absorption spectroscopy and ion chromatography respectively. The average PM₁₀ concentrations varied from 97.2 to 152.5 μg/m³, which were found to be below the Indian air quality standards. While industrial areas had the highest concentrations of heavy metals such as Fe, Zn and Cr and also the $\text{SO}_{4}^{2-}$ ions, traffic areas with relatively higher traffic densities in the city endured highest concentrations of Cd and the $\text{NO}_{3}^{-}$ ion. As gaseous pollutants serve as precursors of ionic particles in the atmospheric environment, gaseous pollution control is necessitated along with particulate with special reference to heavy metal and ion pollution abatement for the sustainable development of Madurai city.