Experimental and kinetic modeling of oxygen-enriched air combustion of paper mill sludge

By thermogravimetric analysis (TGA) study, the characteristics of oxygen-enriched air combustion of paper mill sludge were investigated. Experiments on oxidative of paper mill sludge were performed under different atmospheres at 20 °C/min. There are two distinct decomposition processes were observed from the obtained thermogravimetric curves. One of them centered on 320–350 °C with a weight loss of 50%, the second centered on 780–795 °C with a weight of loss 30%. Shift of oxygen concentration have some influences on decomposition processes, and then the processes of paper mill sludge combustion in oxygen-enriched air can be divided into three stages. The kinetic parameters observed by direct non-linear regressions. At the fixed carbon combustion stage, when oxygen concentration from 20 to 80 vol.%, the apparent activation energy is increased from 52.30 to 123.16 kJ/mol, the reaction order of all runs are around 1.     

Effects of bulking agent addition on odorous compounds emissions during composting of OFMSW

The effects of rice straw addition level on odorous compounds emissions in a pilot-scale organic fraction of municipal solid waste (OFMSW) composting plant were investigated. The cumulative odorous compounds emissions occurred in a descending order of 40.22, 28.71 and 27.83 mg/dry kg of OFMSW for piles with rice straw addition level at ratio of 1:10, 2:10 and 3:10 (mixing ratio of rice straw to OFMSW on a wet basis), respectively. The mixing ratio of rice straw to OFMSW had a statistically significant effect on the reduction of malodorous sulfur compounds emissions, which had no statistically significant effect on the reduction of VFAs, alcohols, aldehydes, ketones, aromatics and ammonia emissions during composting, respectively. The cumulative emissions of malodorous sulfur compounds from piles with the increasing rice straw addition level were 1.17, 1.08 and 0.88 mg/dry kg of OFMSW, respectively. The optimal mixing ratio of rice straw to OFMSW was 1:5. Using this addition level, the cumulative malodorous sulfur compounds emissions based on the organic matter degradation were the lowest during composting of OFMSW.     

Mechanisms contributing to the thermal analysis of waste incineration bottom ash and quantification of different carbon species

The focus of this study was to identify the main compounds affecting the weight changes of bottom ash (BA) in conventional loss on ignition (LOI) tests and to obtain a better understanding of the individual processes in heterogeneous (waste) materials such as BA. Evaluations were performed on BA samples from a refuse derived fuel incineration (RDF-I) plant and a hospital waste incineration (HW-I) plant using thermogravimetric analysis and subsequent mass spectrometry (TG–MS) analysis of the gaseous thermal decomposition products. Results of TG–MS analysis on RDF-I BA indicated that the LOI measured at 550 °C was due to moisture evaporation and dehydration of Ca(OH)₂ and hydrocalumite. Results for the HW-I BA showed that LOI at 550 °C was predominantly related to the elemental carbon (EC) content of the sample. Decomposition of CaCO₃ around 700 °C was identified in both materials. In addition, we have identified reaction mechanisms that underestimate the EC and overestimate the CaCO₃ contents of the HW-I BA during TG–MS analyses. These types of artefacts are expected to occur also when conventional LOI methods are adopted, in particular for materials that contain CaO/Ca(OH)₂ in combination with EC and/or organic carbon, such as e.g. municipal solid waste incineration (MSWI) bottom and fly ashes. We suggest that the same mechanisms that we have found (i.e. in situ carbonation) can also occur during combustion of the waste in the incinerator (between 450 and 650 °C) demonstrating that the presence of carbonate in bottom ash is not necessarily indicative for weathering. These results may also give direction to further optimization of waste incineration technologies with regard to stimulating in situ carbonation during incineration and subsequent potential improvement of the leaching behavior of bottom ash.     

Anaerobic digestion and co-digestion of slaughterhouse waste (SHW): Influence of heat and pressure pre-treatment in biogas yield

Mesophilic anaerobic digestion (34 ± 1 °C) of pre-treated (for 20 min at 133 °C, >3 bar) slaughterhouse waste and its co-digestion with the organic fraction of municipal solid waste (OFMSW) have been assessed. Semi-continuously-fed digesters worked with a hydraulic retention time (HRT) of 36 d and organic loading rates (OLR) of 1.2 and 2.6 kg VS_feed/m³ d for digestion and co-digestion, respectively, with a previous acclimatization period in all cases. It was not possible to carry out an efficient treatment of hygienized waste, even less so when OFMSW was added as co-substrate. These digesters presented volatile fatty acids (VFA), long chain fatty acids (LCFA) and fats accumulation, leading to instability and inhibition of the degradation process. The aim of applying a heat and pressure pre-treatment to promote splitting of complex lipids and nitrogen-rich waste into simpler and more biodegradable constituents and to enhance biogas production was not successful. These results indicate that the temperature and the high pressure of the pre-treatment applied favoured the formation of compounds that are refractory to anaerobic digestion.The pre-treated slaughterhouse wastes and the final products of these systems were analyzed by FTIR and TGA. These tools verified the existence of complex nitrogen-containing polymers in the final effluents, confirming the formation of refractory compounds during pre-treatment.     

Analysis of the combustion and pyrolysis of dried sewage sludge by TGA and MS

In this study, the combustion and pyrolysis processes of three sewage sludge were investigated. The sewage sludge came from three wastewater treatment plants.Proximate and ultimate analyses were performed. The thermal behaviour of studied sewage sludge was investigated by thermogravimetric analysis with mass spectrometry (TGA-MS). The samples were heated from ambient temperature to 800 °C at a constant rate 10 °C/min in air (combustion process) and argon flows (pyrolysis process). The thermal profiles presented in form of TG/DTG curves were comparable for studied sludges. All TG/DTG curves were divided into three stages. The main decomposition of sewage sludge during the combustion process took place in the range 180–580 °C with c.a. 70% mass loss. The pyrolysis process occurred in lower temperature but with less mass loss. The evolved gaseous products (H₂, CH₄, CO₂, H₂O) from the decomposition of sewage sludge were identified on-line.     

Impact of source segregation intensity of solid waste on fuel consumption and collection costs

Fuel consumption and collection costs of solid waste were evaluated by the aid of a simulation model for a given collection area of a medium-sized Italian city. Using the model it is possible to calculate time, collected waste and fuel consumption for a given waste collection route. Starting from the data for the current waste collection scenario with a Source Segregated (SS) intensity of 25%, all the main model error evaluated was ?1.2. SS intensity scenarios of 25%, 30%, 35% and 52% were simulated. Results showed an increase in the average fuel consumed by the collection vehicles that went from about 3.3 L/tonne for 25% SS intensity to about 3.8 L/tonne for a SS intensity of 52%. Direct collection costs, including crews and vehicle purchase, ranged from about 40 €/tonne to about 70 €/tonne, respectively, for 25% and 52% SS intensity. The increase in fuel consumption and collection costs depends on the density of the waste collected, on the collection vehicle compaction ratio and on the waste collection vehicle utilization factor (WCVUF). In particular a reduction of about 50% of the WCVUF can lead to an average increase of about 80% in fuel consumption and 100% in collection costs.     

Production costs and operative margins in electric energy generation from biogas. Full-scale case studies in Italy

The purpose of this study was to observe the economic sustainability of three different biogas full scale plants, fed with different organic matrices: energy crops (EC), manure, agro-industrial (Plants B and C) and organic fraction of municipal solid waste (OFMSW) (Plant A). The plants were observed for one year and total annual biomass feeding, biomass composition and biomass cost (€ Mg^?1), initial investment cost and plant electric power production were registered. The unit costs of biogas and electric energy (€ Sm^?3_biogas, € kW h^?1_EE) were differently distributed, depending on the type of feed and plant. Plant A showed high management/maintenance cost for OFMSW treatment (0.155 € Sm^?3_biogas, 45% of total cost), Plant B suffered high cost for EC supply (0.130 € Sm^?3_biogas, 49% of total cost) and Plant C showed higher impact on the total costs because of the depreciation charge (0.146 € Sm^?3_biogas, 41% of total costs). The breakeven point for the tariff of electric energy, calculated for the different cases, resulted in the range 120–170 € MW h^?1_EE, depending on fed materials and plant scale. EC had great impact on biomass supply costs and should be reduced, in favor of organic waste and residues; plant scale still heavily influences the production costs. The EU States should drive incentives in dependence of these factors, to further develop this still promising sector.     

Physico-chemical analysis and calorific values of poultry manure

Spain is one of the major producers of broilers and laying hens in the European Union, with an overall market share of around 12%. The poultry manure that is produced is usually employed as fertilizer on cropland, either directly or after a composting process. In some cases, however, this waste is transported over 120 km to be used as fertilizer, with the resulting high transport costs. In other countries, poultry manure is used as an alternative natural fuel source for power generation. In this study, poultry manure from all the laying hen farms in Asturias was characterized with a view to its possible use as an energy source. The Higher Heating Values on a dry basis (experimental) varies between 12,052 and 13,882 kJ/kg. Lower Heating Values (LHVs) on a wet basis range are much lower (mean values of 2664 kJ/kg) due to the high moisture content of poultry manure. Accordingly, the co-combustion of this waste with other types of waste such as forest and wood waste (LHV on a wet basis of 8044 and 15,830 kJ/kg, respectively) or municipal solid waste (LHV on a wet basis of 10,725 kJ/kg) should be considered as an alternative energy source. Chlorine and sulphur contents in dry matter vary around mean values of 0.64% and 0.11%, respectively. The waste also presents high amounts of Ca (4.84%) and K (2.38%).     

Leaching behavior of copper from waste printed circuit boards with Brønsted acidic ionic liquid

In this work, a Brønsted acidic ionic liquid, 1-butyl-3-methyl-imidazolium hydrogen sulfate ([bmim]HSO₄), was used to leach copper from waste printed circuit boards (WPCBs, mounted with electronic components) for the first time, and the leaching behavior of copper was discussed in detail. The results showed that after the pre-treatment, the metal distributions were different with the particle size: Cu, Zn and Al increased with the increasing particle size; while Ni, Sn and Pb were in the contrary. And the particle size has significant influence on copper leaching rate. Copper leaching rate was higher than 99%, almost 100%, when 1 g WPCBs powder was leached under the optimum conditions: particle size of 0.1–0.25 mm, 25 mL 80% (v/v) ionic liquid, 10 mL 30% hydrogen peroxide, solid/liquid ratio of 1/25, 70 °C and 2 h. Copper leaching by [bmim]HSO₄ can be modeled with the shrinking core model, controlled by diffusion through a solid product layer, and the kinetic apparent activation energy has been calculated to be 25.36 kJ/mol.     

A comparative study of two composts as filter media for the removal of gaseous reduced sulfur compounds (RSCs) by biofiltration: Application at industrial scale

This work presents the use of two composts as filter media for the treatment by biofiltration of odors emitted during the aerobic composting of a mixture containing sewage sludge and yard waste. The chemical analysis of the waste gas showed that the malodorous compounds at trace level were the reduced sulfur compounds (RSCs) which were dimethyl sulfide (Me₂S), methanethiol (MeSH) and hydrogen sulfide (H₂S). Laboratory tests for biofiltration treatment of RSCs were performed in order to compare the properties of two filter media, consisted of a mature compost with yard waste (YW) and a mixture of mature compost with sewage sludge and yard waste (SS/YW). The maximum elimination capacity (EC) values obtained with the YW mature compost as packing material were 12.5 mg m^?3 h^?1 for H₂S, 7.9 mg m^?3 h^?1 for MeSH and 34 mg m^?3 h^?1 for Me₂S, and the removal efficiency decreased in the order of: H₂S > MeSH > Me₂S. Moreover, the YW compost filter medium had a better behavior than the filter medium based on SS/YW in terms of acclimation of the microbial communities and moisture content. According to these results, a YW mature compost as packing material for an industrial biofilter were designed and this industrial biofilter was found effective under specified conditions (without inoculation and addition of water). The results showed that the maximum EC value of RSCs was 935 mg m^?3 h^?1 (100% removal efficiency, RE) for an inlet loads (IL) between 0 and 1000 mg m^?3 h^?1. Thus, YW compost medium was proven efficient for biofiltration of RSCs both at laboratory and industrial scale.     

Experimental investigation of wood combustion in a fixed bed with hot air

Waste combustion on a grate with energy recovery is an important pillar of municipal solid waste (MSW) management in the Netherlands. In MSW incinerators fresh waste stacked on a grate enters the combustion chamber, heats up by radiation from the flame above the layer and ignition occurs. Typically, the reaction zone starts at the top of the waste layer and propagates downwards, producing heat for drying and devolatilization of the fresh waste below it until the ignition front reaches the grate. The control of this process is mainly based on empiricism.MSW is a highly inhomogeneous fuel with continuous fluctuating moisture content, heating value and chemical composition. The resulting process fluctuations may cause process control difficulties, fouling and corrosion issues, extra maintenance, and unplanned stops. In the new concept the fuel layer is ignited by means of preheated air (T > 220 °C) from below without any external ignition source. As a result a combustion front will be formed close to the grate and will propagate upwards. That is why this approach is denoted by upward combustion.Experimental research has been carried out in a batch reactor with height of 4.55 m, an inner diameter of 200 mm and a fuel layer height up to 1 m. Due to a high quality two-layer insulation adiabatic conditions can be assumed. The primary air can be preheated up to 350 °C, and the secondary air is distributed via nozzles above the waste layer. During the experiments, temperatures along the height of the reactor, gas composition and total weight decrease are continuously monitored. The influence of the primary air speed, fuel moisture and inert content on the combustion characteristics (ignition rate, combustion rate, ignition front speed and temperature of the reaction zone) is evaluated.The upward combustion concept decouples the drying, devolatilization and burnout phase. In this way the moisture and inert content of the waste have almost no influence on the combustion process. In this paper an experimental comparison between conventional and reversed combustion is presented.     

A new method for evaluating the sewage sludge pyrolysis kinetics

A new method to simplify calculation the kinetics model is applied to sewage sludge pyrolysis based on the assumption that volatile run out as soon as it formed and during temperature arising process in this study. Difference method widely used to solve math problems is conducted to calculate kinetics parameters. Pyrolysis experiments are carried out at heating rates of 10, 15, 20, and 50 °C/min. All the TG curves are divided into three parts which are beginning decomposition temperature range, main decomposition temperature range, and final decomposition temperature range. The second one is employed to determine the parameters for more than 70% of the total mass loss occurs in this range. According to the developed method, the react order, reaction energy and pre-exponential factor are obtained, which are in the range of 3.9–4.1, 82.3–109.2 kJ/mol and 7.7 × 10⁶–2.8 × 10⁹/min, respectively, which are in the range of that reported previously. As a comparison experimental data with calculated data, the well fitting results indicate that this method is appropriate for simulating sludge pyrolysis kinetics.     

Quality improvement of pyrolysis oil from waste rubber by adding sawdust

This work was aimed at improving the pyrolysis oil quality of waste rubber by adding larch sawdust. Using a 1 kg/h stainless pyrolysis reactor, the contents of sawdust in rubber were gradually increased from 0%, 50%, 100% and 200% (wt%) during the pyrolysis process. Using a thermo-gravimetric (TG) analyzer coupled with Fourier transform infrared (FTIR) analysis of evolving products (TG–FTIR), the weight loss characteristics of the heat under different mixtures of sawdust/rubber were observed. Using the pyrolysis–gas chromatography (GC)–mass spectrometry (Py–GC/MS), the vapors from the pyrolysis processes were collected and the compositions of the vapors were examined. During the pyrolysis process, the recovery of the pyrolysis gas and its composition were measured in-situ at a reaction temperature of 450 °C and a retaining time of 1.2 s. The results indicated that the efficiency of pyrolysis was increased and the residual carbon was reduced as the percentage of sawdust increased. The adding of sawdust significantly improved the pyrolysis oil quality by reducing the polycyclic aromatic hydrocarbons (PAHs) and nitrogen and sulfur compounds contents, resulting in an improvement in the combustion efficiency of the pyrolysis oil.     

Composition and production rate of medical waste from a small producer in Greece

The objective of this work was to determine the composition and production rate of medical waste from the health care facility of social insurance institute, a small waste producer in Xanthi, Greece. Specifically, produced medical waste from the clinical pathology (medical microbiology) laboratory, the X-ray laboratory and the surgery and injection therapy departments of the health facility was monitored for six working weeks. A total of 240 kg medical solid waste was manually separated and weighed and 330 L of liquid medical waste was measured and classified. The hazardous waste fraction (%w/w) of the medical solid waste was 91.6% for the clinical pathology laboratory, 12.9% for the X-ray laboratory, 24.2% for the surgery departments and 17.6% for the injection therapy department. The infectious waste fraction (%w/w) of the hazardous medical solid waste was 75.6% for the clinical pathology laboratory, 0% for the X-ray laboratory, 100% for the surgery departments and 75.6% for the injection therapy department. The total hazardous medical solid waste production rate was 64 ± 15 g/patient/d for the clinical pathology laboratory, 7.2 ± 1.6 g/patient/d for the X-ray laboratory, 8.3 ± 5.1 g/patient/d for the surgery departments and 24 ± 9 g/patient/d for the injection therapy department. Liquid waste was produced by the clinical pathology laboratory (infectious-and-toxic) and the X-ray laboratory (toxic). The production rate for the clinical pathology laboratory was 0.03 ± 0.003 L/patient/d and for the X-ray laboratory was 0.06 ± 0.006 L/patient/d. Due to the small amount produced, it was suggested that the most suitable management scheme would be to transport the hazardous medical waste, after source-separation, to the Prefectural Hospital of Xanthi to be treated with the hospital waste. Assuming this data is representative of other small medical facilities, medical waste production can be estimated for such facilities distributed around Greece.     

Analysis of the combustion of sewage sludge-derived fuel by a thermogravimetric method in China

The treatment and disposal of sewage sludge are significant environmental problems in China. The reuse of sewage sludge for fuel could be an effective solution. The aim of this study was to characterize the behavior of sludge-derived fuel during combustion by a thermogravimetric method. The combustion profiles obtained showed four obvious weight loss regions. The results of dynamics analysis showed that first-order reactions together with Arrhenius’ law explained reasonably well the different stages of weight loss in the samples. Three temperature regions (162–327 °C, 367–445 °C, and 559–653 °C for sawdust and 162–286 °C, 343–532 °C, and 609–653 °C for coal) in each derivative thermogravimetry (DTG) curve corresponded well with the Arrhenius equation. The reactivity of sludge was lower than that of samples containing sawdust, but higher than that of coal-containing samples. These data demonstrate that sludge-derived fuel has better combustion characteristics than sludge, sawdust, or coal.     

Evolution of butyric acid and the methanogenic microbial population in a thermophilic dry anaerobic reactor

Knowledge of the relationship between the evolution of butyric acid, the main precursor of methane, and the methanogenic microbial population, quantified by fluorescent in situ hybridization (FISH), is important for understating and controlling the anaerobic digestion of solid waste. In this study, a statistical analysis has been made of this relationship in a laboratory-scale continuously stirred tank reactor (CSTR) without recycling of biomass. The CSTR has been operated at four organic loading rates (OLR) between 4.42 and 7.50 kg VS m^?3 day^?1, using the Organic Fraction of Municipal Solid Waste (OFMSW) as the substrate. During the start-up stage, the consumption of butyric acid is related to the population of H₂-utilising methanogens (R² = 0.774), whereas in the stabilization stage, it is related to that of acetoclastic methanogens (R² = 0.716). Therefore, it can be concluded that the methanogenic population dynamics are closely correlated with the concentration of volatile fatty acids, and in particular, with that of butyric acid.     

Thermogravimetric analysis and kinetic study on large particles of printed circuit board wastes

Pyrolysis of large printed circuit board (PCB) waste particle was conducted on a specially designed laboratory-scale thermobalance (Macro-TG) with sample loading of 30 g under dynamic nitrogen atmosphere. The effects of heating rate (10, 15, 20 and 25 °C min^?1) and particle size (1 mm × 1 mm, 5 mm × 5 mm, 10 mm × 10 mm and 10 mm × 20 mm) were examined. To compare the different decomposition behavior of fine and large one, the thermal decomposition of PCB waste powder (approximately 5 mg) was also performed on a thermogravimetric analyzer (common TG) under various heating rates (10, 15, 20 and 40 °C min^?1) and particle size ranges (0.198–0.165 mm, 0.165–0.074 mm, 0.074–0.055 mm and 0.055–0.047 mm). Experimental results show that large particle has a pyrolysis reaction retardancy compared to fine one. The distributed activation energy model was used to study the pyrolysis kinetics. It was found that during pyrolysis process, values of frequency factor (k₀) changed with different activation energy (E) values. On common TG, the E values range from 156.95 to 319.37 kJ mol^?1 and k₀ values range from 2.67 × 10¹³ to 2.24 × 10²⁷ s^?1. While, on Macro-TG, the range of E was 31.48–41.26 kJ mol^?1 and of the frequency factor was 19.80–202.67 s^?1.     

Anaerobic co-digestion of wine/fruit-juice production waste with landfill leachate diluted municipal sludge cake under semi-continuous flow operation

Anaerobic co-digestion of four organic waste streams; a thickened waste activated sludge (TWAS) and screen cake (SC) from a fruit-juice/winery wastewater treatment plant along with municipal sludge cake (MC) and landfill leachate (LL) was evaluated. A total of eight semi-continuously-fed single and co-digesters were operated side-by-side at sludge retention times (SRT) of 20 and 10 days. Co-digestion of industrial waste streams (TWAS and SC) with MC and LL resulted in increased operational stability compared to the single digestion of industrial TWAS at the higher organic loading (10 d SRT). Although digester operational temperature had no statistically significant effect on organics removal and biogas production, mesophilic digesters had consistently higher total coliform densities (8838–37,959 most probable number or MPN/g-dry weight) compared to the thermophilic digesters (41–6723 MPN/g-dry weight) at both SRTs. Coliform analysis results also proved that most of the thermophilic digestates could be classified as Class A biosolids according to regulations. Furthermore, addition of industrial TWAS to co-digesters enhanced the dewaterability of the digested streams. A cost-benefit analysis confirmed the benefits and indicated that a full-scale co-digester utilizing all four waste streams can decrease the total capital and operational cost by 22% ($10.52 million).     

Stabilization of heavy metals in MSWI fly ash using silica fume

The objective of this work was to investigate the feasibility and effectiveness of silica fume on stabilizing heavy metals in municipal solid waste incineration (MSWI) fly ash. In addition to compressive strength measurements, hydrated pastes were characterized by X-ray diffraction (XRD), thermal-analyses (DTA/TG), and MAS NMR (²⁷Al and ²⁹Si) techniques. It was found that silica fume additions could effectively reduce the leaching of toxic heavy metals. At the addition of 20% silica fume, leaching concentrations for Cu, Pb and Zn of the hydrated paste cured for 7 days decreased from 0.32 mg/L to 0.05 mg/L, 40.99 mg/L to 4.40 mg/L, and 6.96 mg/L to 0.21 mg/L compared with the MSWI fly ash. After curing for 135 days, Cd and Pb in the leachates were not detected, while Cu and Zn concentrations decreased to 0.02 mg/L and 0.03 mg/L. The speciation of Pb and Cd by the modified version of the European Community Bureau of Reference (BCR) extractions showed that these metals converted into more stable state in hydrated pastes of MSWI fly ash in the presence of silica fume. Although exchangeable and weak-acid soluble fractions of Cu and Zn increased with hydration time, silica fume addition of 10% can satisfy the requirement of detoxification for heavy metals investigated in terms of the identification standard of hazardous waste of China.     

An LCA model for waste incineration enhanced with new technologies for metal recovery and application to the case of Switzerland

A process model of municipal solid waste incinerators (MSWIs) and new technologies for metal recovery from combustion residues was developed. The environmental impact is modeled as a function of waste composition as well as waste treatment and material recovery technologies. The model includes combustion with a grate incinerator, several flue gas treatment technologies, electricity and steam production from waste heat recovery, metal recovery from slag and fly ash, and landfilling of residues and can be tailored to specific plants and sites (software tools can be downloaded free of charge). Application of the model to Switzerland shows that the treatment of one tonne of municipal solid waste results on average in 425 kg CO₂-eq. generated in the incineration process, and 54 kg CO₂-eq. accrue in upstream processes such as waste transport and the production of operating materials. Downstream processes, i.e. residue disposal, generates 5 kg CO₂-eq. Savings from energy recovery are in the range of 67 to 752 kg CO₂-eq. depending on the assumptions regarding the substituted energy production, while the recovery of metals from slag and fly ash currently results in a net saving of approximately 35 kg CO₂-eq. A similar impact pattern is observed when assessing the MSWI model for aggregated environmental impacts (ReCiPe) and for non-renewable resource consumption (cumulative exergy demand), except that direct emissions have less and no relevance, respectively, on the total score. The study illustrates that MSWI plants can be an important element of industrial ecology as they provide waste disposal services and can help to close material and energetic cycles.