Possibilities of reduction of recipient loading of tannery wastewater in Slovenia

The leather industry is well known as a high consumer of water (30 to 80 m³ for 1 ton of processed raw skins). At the same time this industry is known for the: high specific pollution of wastewater. The main characteristics of tannery wastewater are: high salinity, high organic loading (COD, BOD₅), high content of ammonia and organic nitrogen. and presence of specific pollutants (sulphide, chromium).The largest Slovenian tannery (IUV Vrhnika) processing 40 to 50 t of pig skins daily has a good system of physico-chemical pre-treatment of their wastewater (coagulation and flocculation with AI-sulfate and anionic polyelectrolyte). In pre-treatment, about 60% of organic substances are removed (COD and BOD₅) and above 95% of sulfide and chromium. Concerning Siovenian regulations and taking into consideration the fact that this tannery is located on the relatively small and slowly running river Ljubljanica such pretreatment is not sufficient. The company would like to supplement pre-treatment with biological treatment.Laboratory and pilot scale feasibility experiments including conventional biological treatment with activated sludge and combined anaerobic-anoxic-aerobic treatment with fixed biomass using mechanical pretreated wastewater and pretreated wastewater with flotation were performed. It became clear that effective biological treatment requires long retention times (several days) for applicable effluent.     

Production of porous carbonaceous adsorbent from physical activation of sewage sludge: application to wastewater treatment.

With an objective of production of carbonaceous sorbent for industrial effluent treatment, physical activation by steam of biological sludge collected from the municipal wastewater treatment plant of Nantes (France) was studied and optimised using experimental design. Thus, this activation process consists of a carbonisation under N2 atmosphere at 600 degrees C for 1 h, followed by a thermal oxidation using steam (760 degrees C, 0.5 h, 2.5 L/Umin). The global mass yield of the process is equal to 38%. The thermal treatment allows a specific surface area of up to 225 m2/g to be reached, the porous structure being composed of both micropores and mesopores. The content of acidic surface groups is 0.71 mEq/g whereas that of basic surface groups is 0.55 mEq/g. The adsorption properties of the sorbent made from sludge are estimated with regard to various pollutants representative of industrial pollution of wastewaters and compared with those of commercial activated carbon. Whereas the adsorption capacities of organic micropollutants are quite low because of proportionality to the microporosity, the important mesoporosity of the sorbent leads to interesting properties for macromolecules removal from aqueous solutions, such as dyes (q(m) = 175-200 mg/g). Furthermore, the surface functional groups and Ca2+ ions within the materials allow high copper ion adsorption capacities of 140 mg/g to be obtained. Finally, a techno-economic approach shows that the sludge activation process seems to be economically competitive with regard to incineration.     

Performance evaluation of SBR treatment for nitrogen removal from tannery wastewater.

Performance of SBR treatment for nitrogen removal from tannery is evaluated for a wide range of wastewater temperature between 7 and 30 degrees C. A pilot-scale SBR unit fed with plain-settled wastewater is operated on site for this purpose. Effective nitrogen removal is sustained by adjustment of the sludge age from 28 to 5 days. Concentration profiles of nitrogen compounds within a selected complete SBR cycle during the steady state operation at different wastewater temperatures and sludge ages are evaluated by model simulation. System performance is also interpreted in terms of modeling and stoichiometric calculation. Additional nitrate loss was observed during aerobic period when the aeration intensity was reduced by the factor of 50%.     

Control of C/N ratio for butyric acid production from textile wastewater sludge by anaerobic digestion

Increasing textile wastewaters and their biotreatment byproduct-waste activated sludge are serious pollution problems. Butyric acid production from textile wastewater sludge by anaerobic digestion at different C/N ratios was investigated. Adding starch to textile wastewater sludge with a C/N ratio of 30 increased the butyric acid concentration and percentage accounting for total volatile fatty acids (TVFAs) to 21.42 g/L and 81.5%, respectively, as compared with 21.42 g/L and 10.6% of textile wastewater sludge alone. The maximum butyric acid yield (0.45 g/g VS), conversion rate (0.74 g/g VS(digest)) and production rate (2.25 g/L d) was achieved at a C/N ratio of 30. The biological toxicity of textile wastewater sludge also significantly decreased after the anaerobic digestion. The study indicated that the anaerobic co-digestion of textile wastewater sludge and carbohydrate-rich waste with appropriate C/N ratio is possible for butyric acid production.     

Characterization of cobalt ferrite-supported activated carbon for removal of chromium and lead ions from tannery wastewater via adsorption equilibrium

In this experiment, cobalt ferrite-supported activated carbon (CF-AC) was developed and characterized via the wet impregnation method for the removal of Cr and Pb(II) ions from tannery wastewater. Batch adsorption was carried out to evaluate the effect of experimental operating conditions (pH of solution, contact time, adsorbent dose, and temperature), and the removal efficiencies of Cr and Pb(II) ions by the developed adsorbents were calculated and recorded for all experimental conditions. These variables were estimated and reported as removal efficiencies of 98.2% for Cr and 96.4% for Pb(II) ions at the optimal conditions of 5, 0.8 g, 80 min, and 333 K for pH, adsorbent dose, contact time, and temperature, respectively. The equilibrium for the sorption of Cr and Pb(II) ions was studied using four widely used isotherm models (the Langmuir, Freundlich, Dubinin-Radushkevich, and Temkin isotherm models). It was found that the Freundlich isotherm model fit better with the coefficient of determination (R²) of 0.948 4 and a small sum of square error of 0.000 6. The maximum adsorption capacities (Q_m) of Pb(II) and Cr adsorbed onto CF-AC were determined to be 6.27 and 23.6 mg/g, respectively. The adsorption process conformed well to pseudo-second order kinetics as revealed by the high R² values obtained for both metals. The thermodynamic parameters showed that adsorption of Cr and Pb(II) ions onto CF-AC was spontaneous, feasible, and endothermic under the studied conditions. The mean adsorption energy (E) values revealed that the adsorption mechanism of Cr and Pb(II) by CF-AC is physical in nature. The results of the study showed that adsorbent developed from CF-AC can be efficiently used as an environmentally friendly alternative adsorbent, for removal of Cr and Pb(II) ions in tannery wastewater.     

Enhanced biological wastewater treatment using sodium alginate-immobilized microorganisms in a fluidized bed reactor

In this study, a microbial consortium isolated from an activated sludge tank of a conventional wastewater treatment plant was immobilized using sodium alginate (SA) as a support material for contaminant biodegradation in wastewater. A volume of 500 mL of activated sludge was immobilized in the SA beads (with a mass concentration of 25 g/L). The resulting SA beads were characterized, introduced into a fluidized bed reactor, fed with 1000 mL of the sample, and characterized again after the treatment process. The SA-immobilized microorganisms were tested first for degradation of organic matter (expressed as chemical oxygen demand) and total phosphorous in domestic wastewater, achieving removal efficiencies of 71% and 93%, respectively, after 12 h. Subsequently, the SA-immobilized microorganisms were tested for degradation of a basic blue 9 (BB9) textile dye in a condition that simulated textile wastewater. The efficiency of the BB9 degradation was found to be as high as 99.5% after 2 h. According to these results, SA-immobilized microorganisms were found to be an environmentally friendly and cost-effective alternative for treatment of municipal and industrial wastewater effluents.     

特定污泥对铬(Ⅵ)的吸附容量研究

接种了高效菌种A、B的驯化污泥在前期的生物滤床系统中体现了良好的铬(Ⅵ)去除效率,为了解决系统放大后污泥再生与使用周期等问题,对污泥的铬(Ⅵ)吸附容量进行了测定,测定项目包括一次连续吸附总量、营养添加前后吸附容量的变化等。以铬(Ⅵ)质量浓度为100mg/L的废水进行实验,得到该污泥吸附最佳时间为40min,此时污泥对铬的吸附能力为污泥自身干重的14 94%。一次连续吸附总量为27～28mg/g干污泥。营养液的加入使得污泥吸附能力提高了29 68%。     

Model-based evaluation of nitrogen removal in a tannery wastewater treatment plant.

Computer modelling has been used in the last 15 years as a powerful tool for understanding the behaviour of activated sludge wastewater treatment systems. However, computer models are mainly applied for domestic wastewater treatment plants (WWTPs). Application of these types of models to industrial wastewater treatment plants requires a different model structure and an accurate estimation of the kinetics and stoichiometry of the model parameters, which may be different from the ones used for domestic wastewater. Most of these parameters are strongly dependent on the wastewater composition. In this study a modified version of the activated sludge model No. 1 (ASM 1) was used to describe a tannery WWTP. Several biological tests and complementary physical-chemical analyses were performed to characterise the wastewater and sludge composition in the context of activated sludge modelling. The proposed model was calibrated under steady-state conditions and validated under dynamic flow conditions. The model was successfully used to obtain insight into the existing plant performance, possible extension and options for process optimisation. The model illustrated the potential capacity of the plant to achieve full denitrification and to handle a higher hydraulic load. Moreover, the use of a mathematical model as an effective tool in decision making was demonstrated.     

Evaluation of sludge reduction and phosphorus recovery efficiencies in a new advanced wastewater treatment system using denitrifying polyphosphate accumulating organisms.

A new biological nutrient removal process, anaerobic-oxic-anoxic (A/O/A) system using denitrifying polyphosphate-accumulating organisms (DNPAOs), was proposed. To attain excess sludge reduction and phosphorus recovery, the A/O/A system equipped with ozonation tank and phosphorus adsorption column was operated for 92 days, and water quality of the effluent, sludge reduction efficiency, and phosphorus recovery efficiency were evaluated. As a result, TOC, T-N and T-P removal efficiency were 85%, 70% and 85%, respectively, throughout the operating period. These slightly lower removal efficiencies than conventional anaerobic-anoxic-oxic (A/A/O) processes were due to the unexpected microbial population in this system where DNPAOs were not the dominant group but normal polyphosphate-accumulating organisms (PAOs) that could not utilize nitrate and nitrite as electron acceptor became dominant. However, it was successfully demonstrated that 34-127% of sludge reduction and around 80% of phosphorus recovery were attained. In conclusion, the A/O/A system equipped with ozonation and phosphorus adsorption systems is useful as a new advanced wastewater treatment plant (WWTP) to resolve the problems of increasing excess sludge and depleted phosphorus.     

Integrated chemical, physical and biological processes modelling of anaerobic digestion of sewage sludge.

The biological kinetic processes for anaerobic digestion (AD) are integrated into a two phase subset of a three phase mixed weak acid/base chemistry kinetic model. The approach of characterising sewage sludge into carbohydrates, lipids and proteins, as is done in the International Water Association (IWA) AD model No 1 (ADM1), requires measurements that are not routinely available on sewage sludges. Instead, the sewage sludge is characterised with the COD, carbon, hydrogen, oxygen and nitrogen (CHON) composition and is formulated in mole units, based on conservation of C, N, O, H and COD. The model is calibrated and validated with data from laboratory mesophilic anaerobic digesters operating from 7 to 20 d sludge age and fed a sewage primary and humus sludge mixture. These digesters yielded COD mass balances between 107-109% and N mass balances between 91-99%, and hence the experimental data is accepted as reasonable. The sewage sludge COD is found to be 32-36% unbiodegradable (depending on the kinetic formulation selected for the hydrolysis process) and to have a C3.5H7O2N0.196 composition. For the selected hydrolysis kinetics of surface mediated reaction (Contois), with a single set of kinetic and stoichiometric constants, for all retention times good correlation is obtained between predicted and measured results for: (i) COD; (ii) free and saline ammonia (FSA); (iii) short chain fatty acids (SCFA); (iv) H2CO3 * alkalinity; (v) pH of the effluent stream; (vi) CO2; and (vii) CH4 gases in the gas stream. The measured composition of primary sludge from two local wastewater treatment plants ranged between C3.38H7O1.91 N0.21 and C3.91H7O2.04N0.16. The predicted composition based on mass balances is therefore within 5% of the average measured composition providing persuasive validation of the model.     

Technological transfer to demonstrative scale of sequencing batch biofilter granular reactor (SBBGR) technology for municipal and industrial wastewater treatment

The paper reports the results of an experimental investigation aimed at transferring to demonstrative scale an innovative technology (SBBGR-Sequencing Batch Biofilter Granular Reactor) for the treatment of municipal and industrial wastewater by financial support of the EU Life programme. When this technology was applied for treating municipal wastewater, the results showed that the system was able to remove 80-90% of COD, total suspended solids and ammonia independently of the hydraulic residence time investigated (i.e., from 12 to 4 h). In the case of tannery wastewater, chosen as representative of concentrated industrial wastewater, SBBGR technology was suitable for removing 80-90% of the COD, suspended solids and ammonia content up to organic loading values of 3.5 kg COD/m3.d. During both periods, the process was characterised by a very high sludge age value (theta(c) approximately 150 d) that led to a biomass concentration as high as 35 gTSS/L(bed) and a sludge production much lower (5-6 times lower) that than commonly reported for conventional treatment plants.     

Potentially toxic element release by fenton oxidation of sewage sludge.

The presence, in sewage sludge, of excess levels of the potentially toxic elements (PTE) copper, zinc, chromium, cadmium, nickel, lead and mercury, could impact on our ability to recycle these residues in the future. Far stricter limits on the levels of PTEs are likely in proposed legislation. A method involving the dosing of Fenton's reagent, a mixture of ferrous iron and hydrogen peroxide, under acidic conditions was evaluated for its potential to reduce metal levels. The [Fe]:[H2O2] (w/w) ratio was found to give a good indication of the percentage copper and zinc elution obtainable. Sites with no iron dosing as part of wastewater treatment required extra iron to be added in order to initiate the Fenton's reaction. A significant reduction, in excess of 70%, of the copper and zinc was eluted from both raw primary and activated sludge solid fractions. Cadmium and nickel could be reduced to below detection limits but elution of mercury, lead and chromium was less than 40%. The iron catalyst concentration was found to be a crucial parameter. This process has the potential to reduce the heavy metal content of the sludge and allow the recycling of sludge to continue in a sustainable manner.     

Effect of C/N ratio on nitrous oxide emission from swine wastewater treatment process.

To evaluate control parameters for nitrous oxide (N2O) emissions in the swine wastewater treatment process, the N2O emission was compared in the activated sludge from SBRs acclimated in different carbon/nitrogen (C/N) ratios. N2O emission from a denitrification phase was very strongly dependent on C/N ratio of swine wastewater, and the total N2O emission in the operating condition of BOD5/TN ratio of 2.6 was approximately 270 times greater than that in BOD5/TN ratio of 4.5. However, the effect of C/N ratio on N2O emission amount from nitrification was not significant in an oxic phase study. It is considered that stabilization of the C/N ratio through optimal solid-liquid separation of slurry or use of an external carbon source is indispensable for effective N2O emission control from nitrogen removal process of swine wastewater.     

寿光市城北污水处理厂改良型A~2/O反应池的启动与调试

寿光市城北污水处理厂一期工程处理能力为5万m3/d,以改良型A2/O反应池为核心处理单元,进水中约有60%为工业废水。改良型A2/O反应池的启动调试历时33d,调试结束时,活性污泥性状良好,CODCr、NH3—N、TP完全达到《城镇污水处理厂污染物排放标准》(GB 18918—2002)一级B标准,反硝化作用明显。结果表明,在调试期间,污泥培养方式、内回流比、好氧池DO等对该污水处理厂改良型A2/O反应池处理能力影响比较明显。     

Dewatered alum sludge: a potential adsorbent for phosphorus removal.

Alum sludge refers to the by-product from the processing of drinking water in water treatment works. In this study, groups of batch experiments were designed to identify the characteristics of dewatered alum sludge for phosphorus adsorption. Air-dried alum sludge (moisture content 10.2%), which was collected from a water treatment works in Dublin, was subjected to artificial P-rich wastewater adsorption tests using KH2PO4 as a model P source. Adsorption behaviours were investigated as a function of amount and particle size of alum sludge, pH of solution and adsorption time. The results have shown that pH plays a major role not only in the adsorption process but also in the adsorption capacity. With regard to adsorption capacity, this study reveals the Langmuir adsorption isotherm being the best fit with experimental data (R2 = 0.98-0.99). The maximum adsorption capacities range from 0.7 to 3.5 mg-P/g when the pH of the synthetic P solution was varied from 9.0 to 4.3, accordingly. The outcome of this study indicated that alum sludge is suitable for use as an adsorbent for removal of phosphate from wastewater.     

Integration of chemical and biological oxidation in a SBBR for tannery wastewater treatment.

This paper reports the results of an investigation aimed at evaluating the laboratory-scale performance of an innovative process for treating tannery wastewater. In this process, biological degradation, carried out in a sequencing batch biofilm reactor (SBBR), is combined with chemical oxidation by ozone. Tannery wastewater treatment was carried out, at laboratory scale, on a real primary effluent coming from a centralised plant treating wastewater produced by a large tannery district in Northern Italy. SBBR performance both without and with ozonation, was assessed with very satisfactory results. In particular, in the latter instance the recorded COD, TKN and TSS average removals, (96%), (92%) and (98%) respectively, allowed the maximum allowable concentration values fixed by the Italian regulation in force to be achieved without any additional polishing step. During the investigation biofilm properties (biofilm concentration and biofilm density) and flow dynamics aspects (head loss, shear stress, bed porosity) were also studied. A major feature of the process is that, with or without ozonation, it was characterised by very low specific sludge production (0.05 kgVSS/kgCODremoved) and high biofilm density (i.e. 87-122 gVSS/Lsludge) both contributing to a rather high biofilm concentration (i.e. 31-44 gTSS/Lfilter).     

A novel process for organic acids and nutrient recovery from municipal wastewater sludge.

In this paper, a novel process for organic acids and nutrient recovery from municipal sludge was introduced and evaluated based on laboratory-scale studies. An economical estimation for its practical application was also performed by mass balance in a full-scale plant (Q=158,000 m3 d(-1)). This novel process comprises an upflow sludge blanket-type high performance elutriated acid fermenter (5d of SRT) for organic acids recovery followed by an upflow-type crystallisation (3 h of HRT) reactor using waste lime for nutrient recovery. In the system, the fermenter is characterised by thermophilic (55 degrees C) and alkaline conditions (pH 9), contributing to higher hydrolysis/acidogenesis (0.18 g VFA(COD) g(-1) VSS(COD), 63.3% of VFA(COD)/COD produced, based on sludge characteristics of the rainy season) and pathogen-free stabilised sludge production. It also provides the optimal condition for the following crystallisation reactor. In the process, the waste lime, which is an industrial waste, can be used for pH control and cation (Ca and Mg) sources for crystallisation reaction. A cost estimation for full-scale application demonstrates that this process has economic benefits (about 67 dollars per m3 of wastewater except for the energy expense) even in the rainy season.     

非活性红色链霉菌吸附废水中Pb2+机理分析

采用吸附等温方程、扫描电镜以及红外光谱仪等测试分析方法对红色链霉菌废菌体吸附废水中Pb2+的机理进行分析和探讨。结果表明,强碱的处理可以明显提高废菌体的吸附性能;红色链霉菌细胞壁上的—COO—、C—H和O—H可能是吸附铅离子的主要基团;红色链霉菌吸附Pb2+的过程可能是一个以表面络合反应为主的物理化学吸附过程。     

The role of sludge conditioning and dewatering in the fate of nonylphenol in sludge-amended soils.

One of the main concerns associated with the recycling of biosolids to arable land is their contamination by organic pollutants, like endocrine disruptors. Conditioning and dewatering are usually the last steps of the sewage sludge treatment, before its further utilization. The choice of the specific conditioning/dewatering method may have an effect, not only on the amount of residues in the biosolids, but also on the fate of these compounds in amended soils. Anaerobically digested wastewater sludge was conditioned at lab-scale by means of physical and chemical methods and subsequently dewatered by centrifugation. The produced biosolids plus non-conditioned and non-dewatered sludges were amended separately to soil and spiked with 14C radiolabelled single isomer of nonylphenol. The persistence and leaching potential of nonylphenol after an incubation period of three months were correlated to the sludge treatment method. In comparison to non-conditioned sludge, 54% and 72% higher amount of pollutant residues were extractable when freeze-thawed and limed sludge, respectively, were used. Conditioning of sludge with cationic polymer decreased the leaching potential of nonylphenol in sludge-amended soils, while liming increased it. Fractions of the model compound recovered as extractable and bound residues were analyzed in order to interpret nonylphenol fate.     

Upgrading of Florence wastewater treatment plant: co-digestion and nitrogen autotrophic removal.

In recent years a completely autotrophic nitrogen removal process based on Anammox biomass has been tested in a few European countries in order to treat anaerobic supernatant and to increase the COD/N ratio in municipal wastewater. This work reports experimental results on a possible technical solution to upgrade the S. Colombano treatment plant which treats wastewater from the Florentine urban area. The idea is to use 50% of the volume of the anaerobic digester in order to treat external sewage sludge (as septic tank sludge) together with waste activated sludge and to treat the resulting effluent on a SHARON-ANAMMOX process in order to remove nitrogen from the anaerobic supernatant. Anaerobic co-digestion, tested in a 200 L pilot plant, enables low cost treatment of septic tank sludge and increases biogas production; however, it also increases the nitrogen load re-circulated to the WWTP, where nitrogen removal efficiency is already low (<50%), due to the low COD/N ratio, which limits predenitrification efficiency. Experimental results from a SHARON process tested in a lab-scale pilot plant show that nitrite oxidising bacteria are washed-out and steady nitrite production can be achieved at retention times in the range 1 - 1.5 days, at 35 degrees C. In a lab-scale SBR reactor, coupled with a nitration bioreactor, maximum specific nitrogen removal rate under nitrite-limiting conditions (with doubling time equal to about 26 days at 35 degrees C) was equal to 0.22 kgN/kgSSV/d, about 44 times the rate measured in inoculum Anammox sludge. Finally, a cost analysis of the proposed upgrade is reported.