Growth responses and metal accumulation capabilities of woody plants during the phytoremediation of tannery sludge

Five woody plants species (i.e. Terminalia arjuna, Prosopis juliflora, Populus alba, Eucalyptus tereticornis and Dendrocalamus strictus) were selected for phytoremediation and grow on tannery sludge dumps of Common Effluent Treatment Plant (CETP), Unnao (Uttar Pradesh), India. Concentration of toxic metals were observed high in the raw tannery sludge i.e. Fe-1667 > Cr-628 > Zn-592 > Pb-427 > Cu-354 > Mn-210 > Cd-125 > Ni-76 mg kg⁻¹ dw, respectively. Besides, physico-chemical properties of the raw sludge represented the toxic nature to human health and may pose numerous risks to local environment. The growth performances of woody plants were assessed in terms of various growth parameters such as height, diameter at breast height (DBH) and canopy area of plants. All the plant species have the capabilities to accumulate substantial amount of toxic metals in their tissues during the remediation. The ratio of accumulated metals in the plants were found in the order Fe > Cr > Mn > Pb > Zn > Cu > Cd > Ni and significant changes in physico-chemical parameters of tannery sludge were observed after treatment. All the woody plants indicated high bioconcentration factor for different metals in the order Fe > Cr > Mn > Ni > Cd > Pb > Zn > Cu. After one year of phytoremediation, the level of toxic metals were removed from tannery sludge up to Cr (70.22)%, Ni (59.21)%, Cd (58.4)%, Fe (49.75)%, Mn (30.95)%, Zn (22.80)%, Cu (20.46)% and Pb (14.05)%, respectively.     

The potential of foliar treatments for enhanced phytoextraction of heavy metals from contaminated soil

Phytoextraction is the plant‐based removal of inorganic contaminants from the soil by root absorption and subsequent translocation to harvestable plant parts. The efficiency of this technique is limited by the phytoavailability of these contaminants in the soil and the root‐to‐shoot transport. To enhance the phytoextraction efficiency, the use of soil amendments has been widely investigated. Potential risks such as increased ecotoxicological effects and leaching of mobilized contaminants caution against the use of persistent mobilizing agents. The potential use of foliar amendments to enhance mineral absorption and/or translocation offers prospects for complementing or substituting soil amendments for enhanced phytoextraction purposes. This study presents an explorative screening to evaluate the feasibility of this approach. Helianthus annuus giganteus plants were grown in moderately contaminated dredged sediment for ten weeks, with daily foliar treatments from week six onward: (1) distilled water (control), (2) magnesium‐ethylenediaminetetraacetic acid (Mg‐EDTA), (3) diethylenetriaminepentaacetic acid (DTPA), (4) nitrilotriacetic acid (NTA), (5) citric acid, (6) oxalic acid, (7) calcium acetate, (8) ammonium thiocyanate (NH₄SCN), and (9) cystein. Applied doses varied between treatments based on plant tolerance: 15 μmol per plant for cystein, 60 μmol per plant for DTPA and NH₄SCN, 180 μmol per plant for Mg‐EDTA and NTA and 400 μmol per plant for the organic acids. At the end of the experiment, shoot accumulation of cadmium, chromium, copper, iron, manganese, nickel, lead, and zinc was evaluated. © 2004 Wiley Periodicals, Inc.     

Effect of different tannery sludge compost amendment rates on growth,biomass accumulation and yield responses of Capsicum plants

Composting has been recognized as one of the most cost effective and environmentally sound alternatives for organic wastes recycling from long and composted wastes have a potential to substitute inorganic fertilizers. We investigated the potential of composted tannery sludge for ornamental purposes and to examine the effects of two different composts and concentrations on ornamental Capsicum growth. The two composts were produced with tannery sludge and the composition of each compost was: compost₁ of tannery sludge (C₁TS) – tannery sludge + sugarcane straw and cattle manure mixed in the ratio 1:3:1 (v:v:v); compost₂ of tannery sludge (C₂TS) – tannery sludge + “carnauba” straw and cattle manure in the ratio 1:3:1 (v:v:v). Each compost was amended with soil at rates (% v:v) of 0%, 25%, 50%, 75% and 100% (designation hereafter as T₁–T₅, respectively). The number of leaves and fruits were counted, and the stem length was also measured. Chlorophyll content was recorded on three leaves of each harvested plant prior to harvest. Number of leaves and fruits, stem length, dry weight of shoot and roots did not vary significantly between the plants grown in two tannery composts. All the treatments with composted tannery sludge application (T₂–T₅) significantly increased the number of leaves and fruits, stem length and chlorophyll content compared with the control (T₁). The chlorophyll content was higher in plants growing in the C₁TS compared to C₂TS. The results of the present study further suggest that Capsicum may be a good option to be grown on composted tannery amended soil.     

Vitrification as an alternative to landfilling of tannery sewage sludge

Due to high content of heavy metals such as chromium, tannery sewage sludge is a material which is difficult to be biologically treated as it is in the case of organic waste. Consequently, a common practice in managing tannery sewage sludge is landfilling. This poses a potential threat to both soil and water environments and it additionally generates costs of construction of landfills that meet specific environment protection requirements. Vitrification of this kind of sewage sludge with the addition of mineral wastes can represent an alternative to landfilling.The aim of this study was to investigate the possibility of obtaining an environmentally safe product by means of vitrification of tannery sewage sludge from a flotation wastewater treatment process and chemical precipitation in order to address the upcoming issue of dealing with sewage sludge from the tannery industry which will be prohibited to be landfilled in Poland after 2016. The focus was set on determining mixtures of tannery sewage sludge with additives which would result in the lowest possible heavy metal leaching levels and highest hardness rating of the products obtained from their vitrification.The plasma vitrification process was carried out for mixtures with various amounts of additives depending on the type of sewage sludge used. Only the materials of waste character were used as additives.One finding of the study was an optimum content of mineral additives in vitrified mixture of 30% v/v waste molding sands with 20% v/v carbonate flotation waste from the zinc and lead industry for the formulations with flotation sewage sludge, and 45% v/v and 5% v/v, respectively, for precipitation sewage sludge. These combinations allowed for obtaining products with negligible heavy metal leaching levels and hardness similar to commercial glass, which suggests they could be potentially used as construction aggregate substitutes. Incineration of sewage sludge before the vitrification process lead to increased hardness of the vitrificates and reduced leaching of some heavy metals.     

Thermal behaviour of chromium electroplating sludge

Galvanic sludge is classified as a hazardous waste and incineration is one of the techniques used for its treatment. The aim of this work is to study the thermal behavior of a galvanic sludge which contains only chromium as a restriction metal. Simultaneous DTA/TG coupled with mass spectrometer tests were performed to characterize the thermal behavior of the sludge. Besides thermal analysis, sludge samples were heated in a specially designed furnace and these samples were submitted to X-ray diffraction. Vapor from the heated sludge was condensed and the particles were analyzed by EDS microprobe coupled in a scanning electron microscope. The slag formed after the calcination of the galvanic sludge was mainly composed of a mixture of calcium phosphate and fluoride. and minor concentrations of metals. A total weight loss of 34% was observed. The greatest part of this weight loss corresponds to CO2, H2O and SO2. H2O is liberated in the temperature range of 500-1,250 degrees C. CO2 in the range of 500-750 degrees C and SO2 near 1,000 degrees C. Chromium evaporation was not observed in relevant quantities, about 99.6% of the Cr remained incorporated in the slag.     

Heavy metal removal from contaminated sludge for land application: a review

In recent years, various methods for heavy metal removal from sewage sludge have been extensively studied in order to minimize the prospective health risks of sludge during land application. In this paper, a comparative review and critical analysis of the application of chemical extraction, bioleaching, electroreclamation, and supercritical fluid extraction (SFE), in removing heavy metals from contaminated sludges is presented. Moreover, speciation studies, which can indicate ease of leachability of the different forms of heavy metals in sludge, are also presented. Experimental studies revealed a broad range in metal extraction efficiencies of the different extraction technologies. Acid treatment seemed to effectively remove Cd, attaining as much as 100% removal for some studies, as compared to bioleaching. SFE also gave higher removal efficiency than bioleaching. Cr, Pb and Ni seemed to be also effectively removed by the acid treatment. For the removal of Cu, Mn and Zn, the bioleaching process seemed to be appropriate with maximum removal efficiencies of 91%, 93% and 96% for the three metals, respectively, and as high as 64% minimum removal efficiency for Zn. The SFE process also gave good results for Cu, Mn and Zn removal. Electroreclamation exhibited better removal efficiency for Mn, but is still inferior to acid treatment and bioleaching processes. For chemical extraction, because of the adverse impacts that can result from the use of inorganic acids and complexing agents, interest can be directed more toward utilizing organic acids as extracting agents because of their biodegradability and capability to remove metals at mildly acidic condition, hence requiring less acid. The bioleaching process, although it seems to give a higher yield of metal extraction with lower chemical cost than chemical extraction, may be limited by the inability of the system to cope with the natural environmental conditions, requires strict monitoring of aeration rate and temperature and has applicability to only low sludge solids concentration. A full-scale study would be useful to better assess the efficiency of the process. The electroreclamation technology is limited by its relatively higher energy consumption and limited applicability to sludge. The SFE method, on the other hand, is limited by the complexity of the process and the cost of ligands suitable for effective metal extraction. Both of these technologies are still in their early stage of application and hence there is a need for further basic and applied studies. Finally, the common advantage for almost all treatment technologies studied is that the extraction efficiencies for some metals are high enough to remove metals from sludge to levels suitable for land application.     

A study of heavy metals and their fate in the composting of tannery sludge

Tannery waste is categorized as toxic and hazardous in Malaysia due to its high content of Cr (in excess of 500 mg/kg) and other heavy metals. Heavy metals, when in high enough concentrations, have the potential to be both phytotoxic and zootoxic. Heavy metals are found as contaminants in tannery sludge. This investigation aimed to identify the fate of chromium, cadmium, copper, lead, and zinc concentrations in tannery sludge throughout a 50-day composting cycle. The results of this study showed a general increase in the removal of Cr, Cd, Pb, and to a much smaller extent Zn and Cu, manifested by a decrease in their overall concentrations within the solid fraction of the final product (the decreases were likely the result of leaching). Furthermore, in using a sequential extraction method for sludge composting at different phases of treatment, a large proportion of the heavy metals were found to be associated to the residual fraction (70-80%) and fractions more resistant to extraction, X-NaOH, X-EDTA, X-HNO3 (12-29%). Less than 2% of the metals were bound to bioavailable fractions X-(KNO3+H2O).     

On the understanding and control of the spontaneous heating of dried tannery wastewater sludge

We studied the spontaneous heating of dried sludge produced by treating wastewater mainly originating from tanneries. Heating up to burning has been observed in the presence of air and moisture, starting at ambient temperature. To understand and prevent the process we combined chemical and morphological analyses (ESEM) with thermal activity monitoring in insulated vessels. Selective additions of chemicals, either to amplify or depress the reactivity, have been used to investigate and identify both the chemical mechanism causing the sludge self-heating, and a prevention or a mitigation strategy. FeS additions accelerate the onset of reactivity, while S sustains it over time. On the contrary, Ca(OH)₂, Na₂CO₃, NaHCO₃, FeCl₂, EDTA, NaClO can limit, up to completely preventing, the exothermic activity. All the experimental evidences show that the reactions supporting the dried sludge self-heating involve the Fe/S/O system. The total suppression of the reactivity requires amounts of additives that are industrially incompatible with waste reduction and economics. The best prevention requires reduction or removal of S and Fe from the dried solid matrix.     

铬渣的无害化处理和综合利用

铬渣产量大、毒性剧烈,是严重污染生态环境和危害人类健康的危险废物.介绍了铬渣各种无害化处理方法的解毒机理、工艺过程和应用实践,阐述了对铬渣进行综合利用的途径,并就铬渣的防治前景提出了建议.     

Organics removal from landfill leachate and activated sludge production in SBR reactors

This study is aimed at estimating organic compounds removal and sludge production in SBR during treatment of landfill leachate. Four series were performed. At each series, experiments were carried out at the hydraulic retention time (HRT) of 12, 6, 3 and 2d. The series varied in SBR filling strategies, duration of the mixing and aeration phases, and the sludge age. In series 1 and 2 (a short filling period, mixing and aeration phases in the operating cycle), the relationship between organics concentration (COD) in the leachate treated and HRT was pseudo-first-order kinetics. In series 3 (with mixing and aeration phases) and series 4 (only aeration phase) with leachate supplied by means of a peristaltic pump for 4h of the cycle (filling during reaction period) - this relationship was zero-order kinetics. Activated sludge production expressed as the observed coefficient of biomass production (Y(obs)) decreased correspondingly with increasing HRT. The smallest differences between reactors were observed in series 3 in which Y(obs) was almost stable (0.55-0.6 mg VSS/mg COD). The elimination of the mixing phase in the cycle (series 4) caused the Y(obs) to decrease significantly from 0.32 mg VSS/mg COD at HRT 2d to 0.04 mg VSS/mg COD at HRT 12d. The theoretical yield coefficient Y accounted for 0.534 mg VSS/mg COD (series 1) and 0.583 mg VSS/mg COD (series 2). In series 3 and 4, it was almost stable (0.628 mg VSS/mg COD and 0.616 mg VSS/mg COD, respectively). After the elimination of the mixing phase in the operating cycle, the specific biomass decay rate increased from 0.006 d(-1) (series 3) to 0.032 d(-1) (series 4). The operating conditions employing mixing/aeration or only aeration phases enable regulation of the sludge production. The SBRs operated under aerobic conditions are more favourable at a short hydraulic retention time. At long hydraulic retention time, it can lead to a decrease in biomass concentration in the SBR as a result of cell decay. On the contrary, in the activated sludge at long HRT, a short filling period and operating cycle of the reactor with the mixing and aeration phases seem the most favourable.     

镍对活性污泥生物除磷的影响及其机理

以实际生活污水为研究对象,在序批式活性污泥反应器中探究了Ni2+对活性污泥形态及生物除磷性能的影响。实验结果表明,Ni2+能够抑制生物除磷,当Ni2+质量浓度由0 mg/L增加至10.0 mg/L时,PO43--P去除率由93%下降至12%。机理研究结果表明：Ni2+能抑制聚磷微生物的厌氧释磷和好氧吸磷,并能抑制内聚物聚羟基烷酸酯（PHA）的合成;当Ni2+质量浓度为10.0 mg/L时,PHA的最大含量仅为2.4 mmol/g （以单位质量挥发性悬浮物所含PHA中C的物质的量计）,远低于空白组中PHA的含量。此外,Ni2+还对微生物群落的组成产生影响,并促进活性污泥中聚糖微生物的增殖。     

Characteristics of carbonized sludge for co-combustion in pulverized coal power plants

Co-combustion of sewage sludge can destabilize its combustion profile due to high volatility, which results in unstable flame. We carried out fuel reforming for sewage sludge by way of carbonization at pyrolysis temperature of 300-500 °C. Fuel characteristics of carbonized sludge at each temperature were analyzed. As carbonization temperature increased, fuel ratio increased, volatile content reduced, and atomic ratio relation of H/C and O/C was similar to that of lignite. The analysis result of FT-IR showed the decrease of aliphatic C-H bond and O-C bond in carbonization. In the analysis result of TG-DTG, the thermogravimetry reduction temperature of carbonized sludge (CS400) was proven to be higher than that of dried sludge, but lower than that of sub-bituminous coal. Hardgrove grindability index increased in proportion to fuel ratio increase, where the carbonized sludge value of 43-110 was similar or higher than the coal value of 49-63. As for ash deposits, slagging and fouling index were higher than that of coal. When carbonized sludge (CS400) and coal were co-combusted in 1-10% according to calorific value, slagging tendency was low in all conditions, and fouling tendency was medium or high according to the compositions of coal.     

燃煤电厂烟气中汞控制技术研究

介绍了溶解法、吸附法、化学法和鳌合法等4种燃煤电厂烟气脱汞技术。从机理上分析了烟气脱汞技术的工艺过程,对脱汞技术的进一步开发和工业化进程具有促进作用。     

Cr（Ⅵ）对活性污泥系统反硝化过程的影响

采用反硝化反应器,研究了Cr（Ⅵ）对活性污泥系统反硝化过程的影响。在进水Cr（Ⅵ）投加量2.5 mg/L条件下,活性污泥反硝化过程中COD和硝酸盐氮的去除率受到的影响较小,而在10.0 mg/L条件下受到的影响较大,COD和硝酸盐氮的去除率分别从最初的97.1%和99.0%降至70.6%和24.7%。在停止投加Cr（Ⅵ）后的恢复期内,反硝化系统可以逐渐恢复对COD和硝酸盐氮的去除,亚硝酸盐氮仍会有积累,但随着时间的延长可恢复至初始状态。硝酸盐氮还原为亚硝酸盐氮的过程比亚硝酸盐氮的还原过程更易受到Cr（Ⅵ）的影响。     

Rapid-extraction oxidation process to recover and reuse copper chromium and arsenic from industrial wood preservative sludge

Chromated copper arsenate (CCA) wood preservative can form insoluble sludges when the hexavalent chromium component is reduced by wood extractives, wood particles and preservative additives in the solution. This sludge accumulates in treating solution work tanks, sumps and in-line filters and must be disposed of as hazardous wastes by waste disposal companies at high costs. A number of commercial sludges were investigated and found to contain 18-94% copper, chromium and arsenic as oxides combined with sand, oil, wood particles, additives and wood extractives. We have developed a multi-stage recycling process whereby approximately 97% of the CCA components are recovered from the sludge. It involves extraction with sodium hypochlorite to remove and oxidize chromium (more than 90%) and extract most of the arsenic (approx. 80%) followed by extraction of the copper and remaining arsenic and chromium with phosphoric acid. The phosphoric acid extract contains some trivalent chromium, which is subsequently oxidized by sodium hypochlorite. The combined oxidized extract containing CrVI, CuII and AsV was compatible with CCA treating solutions and could be re-used commercially for treating wood without having a significant effect on the preservative fixation rate or the leach resistance of the treated wood. A cost analysis showed that the economic savings from recovery of CCA chemicals and reduced landfill costs exceeded the variable costs for materials and energy for the process by as much as Can $966 per tonne of sludge if sodium sulfite can be acquired in bulk quantities for the process.     

Organic and nitrogen removal from landfill leachate in aerobic granular sludge sequencing batch reactors

Granule sequencing batch reactors (GSBR) were established for landfill leachate treatment, and the COD removal was analyzed kinetically using a modified model. Results showed that COD removal rate decreased as influent ammonium concentration increasing. Characteristics of nitrogen removal at different influent ammonium levels were also studied. When the ammonium concentration in the landfill leachate was 366 mg L⁻¹, the dominant nitrogen removal process in the GSBR was simultaneous nitrification and denitrification (SND). Under the ammonium concentration of 788 mg L⁻¹, nitrite accumulation occurred and the accumulated nitrite was reduced to nitrogen gas by the shortcut denitrification process. When the influent ammonium increased to a higher level of 1105 mg L⁻¹, accumulation of nitrite and nitrate lasted in the whole cycle, and the removal efficiencies of total nitrogen and ammonium decreased to only 35.0% and 39.3%, respectively. Results also showed that DO was a useful process controlling parameter for the organics and nitrogen removal at low ammonium input.     

Bacterial composting of animal fleshing generated from tannery industries

Animal fleshing (ANFL) is the major proteinaceous solid waste generated during the manufacture of leather, which requires to be disposed of by environmentally sound manner. This study reports about the treatment of ANFL into an organic compost and its effects on physiological parameters of different crops in a laboratory study. The ANFL was hydrolysed using Selenomonas ruminantium HM000123 and then the hydrolysed ANFL was mixed with cow dung and leaf litter for producing composted organic fertilizer (COF). The COF was characterized for pH, electrical conductivity (EC), total Kjeldhal nitrogen (TKN), and total organic carbon (TOC). The composting resulted in a significant reduction in pH, TOC and C:N ratio and an increase in TKN after 49 days in a compost reactor. Scanning electron microscope and FT-IR were used to analyse the hydrolysis of intra structural ANFL matrix and changes in the functional groups, respectively, in initial and final day COF. Thermogravimetry (TG) analysis was carried out for the raw mixture and COF samples to identify the weight loss under the nitrogen environment. The relative seed germination was found to be 94% in tomato (Lycopersicon esculentum), 92% in green gram (Vigna radiata), 86% in bottle gourd (Lagenaria siceraria (Mol.) Standl.) and 84% in cucumber (Cucumis sativus L.) using the extracts of COF. The results indicate that the combination of both hydrolysis and bacterial composting reduced the overall time required for composting and producing a nutrient-enriched compost product.     

Volatility of heavy metals during incineration of tannery sludge in the presence of chlorides and phosphoric acid.

Knowledge of the behaviour of heavy metals in the combustion process is a most important factor in selecting disposal alternatives for waste materials. Accordingly, in this work, the vaporization behaviour of highly concentrated heavy metals (Pb, Zn, Cu and Cr) in tannery sludge were investigated experimentally. The sludge was spiked with various chlorine compounds (i.e. PVC, FeCl3, CaCl2 and NaCl) and pre-treated with phosphoric acid in order to evaluate the capacity of enhancement and weakening of the volatility of the heavy metals contained in tannery sludge. The experimental results show that the vaporization percentages increased with increasing ratio of Cl/sludge and temperature, and the accelerating and increasing effect of the addition of chlorides on the vaporization percentage of heavy metals was dependent on the release capacity of chlorine radicals. The vaporization percentages of lead and zinc increased by 15-20%, whereas those of copper and chromium increased by only about 3 and 10% at 800 degrees C. However, heavy metals were not expected to be completely released in the combustion process in spite of the high ratio of Cl/sludge. Alternately, heavy metals contained in tannery sludge can be immobilized effectively by pre-treatment with phosphoric acid. When the 85% phosphoric acid accounted for 10% of dry basis of tannery sludge, the phosphate-treated sludge showed the lowest vaporization percentage of about 3-15% with formation of Ca18Cu3(PO4)14, Ca9Cr(PO4)7, Ca19Zn2(PO4)14 and PbMgP2O7 in the bottom ash.