Adsorption of Oxyanions from Industrial Wastewater using Perlite-Supported Magnetite.

Most studies on oxyanion adsorption focus on their removal from synthetic solutions. It is often claimed that the considered adsorbents can be used to treat real (industrial) wastewaters, but this is seldom tested. Perlite-supported magnetite was characterized first by determining its specific surface area, magnetite content and by examining the coating. Tests on a synthetic solution showed that at the ideal pH values (pH 3 to 5), the order of adsorption is Mo(VI) > As(V) > Sb(V) > Cr(VI) > Se(VI). Most oxyanions can be removed for more than 75% with an adsorbent dosage of 1 g/l. Furthermore, perlite-supported magnetite has a higher removal efficiency for oxyanions than commercially available adsorbents and comparable adsorbents described in literature. Perlite-supported magnetite is suitable for treating real wastewaters: it can remove several oxyanions simultaneously from the considered industrial wastewater, but the adsorption order changes due to the presence of interfering anions.

Metal release from contaminated estuarine sediment under pH changes in the marine environment.

The contaminant release from estuarine sediment due to pH changes was investigated using a modified CEN/TS 14429 pH-dependence leaching test. The test is performed in the range of pH values of 0-14 using deionised water and seawater as leaching solutions. The experimental conditions mimic different circumstances of the marine environment due to the global acidification, carbon dioxide (CO2) leakages from carbon capture and sequestration technologies, and accidental chemical spills in seawater. Leaching test results using seawater as leaching solution show a better neutralisation capacity giving slightly lower metal leaching concentrations than when using deionised water. The contaminated sediment shows a low base-neutralisation capacity (BNCpH 12 = -0.44 eq/kg for deionised water and BNCpH 12 = -1.38 eq/kg for seawater) but a high acid-neutralisation capacity when using deionised water (ANCpH 4 = 3.58 eq/kg) and seawater (ANCpH 4 = 3.97 eq/kg). Experimental results are modelled with the Visual MINTEQ geochemical software to predict metal release from sediment using both leaching liquids. Surface adsorption to iron- and aluminium-(hydr)oxides was applied for all studied elements. The consideration of the metal-organic matter binding through the NICA-Donnan model and Stockholm Humic Model for lead and copper, respectively, improves the former metal release prediction. Modelled curves can be useful for the environmental impact assessment of seawater acidification due to its match with the experimental values.

Thermal treatment of solid waste in view of recycling: Chromate and molybdate formation and leaching behaviour.

Elevated Cr and Mo concentrations are often found in leachates of thermally treated solid waste, but there is no general explanation for this so far. Therefore, we studied the leaching behaviour after thermal treatment as a function of heating temperature and residence time for two types of solid waste: contaminated sludge and bottom ash from municipal solid waste incineration. The leaching behaviour of both waste streams was compared with experiments on synthetic samples, allowing deduction of a general mechanism for Cr and Mo leaching. Cr and Mo showed a similar leaching behaviour: after an initial increase, the leaching decreased again at higher temperatures. Oxidation of these elements from their lower oxidation states to chromate and molybdate at temperatures up to 600 °C was responsible for the increased leaching. At higher temperatures, both Mo and Cr leaching decreased again owing to the formation of an amorphous phase, incorporating the newly formed chromate and molybdate salts, which prevents them from leaching.

Heating temperature dependence of Cr(III) oxidation in the presence of alkali and alkaline earth salts and subsequent Cr(VI) leaching behavior.

In this paper, the temperature dependence of Cr(III) oxidation in high temperature processes and the subsequent Cr(VI) leaching was studied using synthetic mixtures. It was experimentally shown that in the presence of alkali and alkaline earth salts, oxidation of Cr(III) takes place, consistent with thermodynamic calculations. Heating of synthetic mixtures of Cr2O3 and Na, K, or Ca salts led to elevated leaching of Cr(VI); in the presence of Na, more than 80% of the initial Cr(III) amount was converted to Cr(VI) at 600-800 °C. Kinetic experiments allowed explanation of the increase in Cr(VI) leaching for increasing temperatures up to 600-800 °C. After reaching a maximum in Cr(VI) leaching at temperatures around 600-800 °C, the leaching decreased again, which could be explained by the formation of a glassy phase that prevents leaching of the formed Cr(VI). By way of illustration, Cr(VI) formation and leaching was evaluated for a case study, the fabrication of ceramic material from contaminated sludge. Based on the proposed reaction mechanisms, countermeasures to prevent Cr oxidation (addition of NH4H2PO4, heating under inert atmosphere) were proposed and successfully tested for synthetic mixtures and for the case study.

Removal of molybdate anions from water by adsorption on zeolite-supported magnetite.

Industrial wastewater may contain high molybdenum concentrations, making treatment before discharge necessary. In this paper, the removal of molybdate anions from water is presented, using clinoptilolite zeolite coated with magnetite nanoparticles. In batch experiments the influence of pH, ionic strength, possible interfering (oxy)anions, temperature and contact time is investigated. Besides determination of kinetic parameters and adsorption isotherms, thermodynamic modeling is performed to get better insight into the adsorption mechanism; molybdenum is assumed to be adsorbed as a FeOMoO2(OH).2H2O inner-sphere complex. At the optimum pH of 3, the adsorption capacity is around 18 mg molybdenum per gram adsorbent. The ionic strength of the solution has no influence on the adsorption capacity. Other anions, added to the molybdenum solution in at least a tenfold excess, only have a minor influence on the adsorption of molybdenum, with the exception of phosphate. Adsorption increases when temperature is increased. It is demonstrated that the adsorbent can be used to remove molybdenum from industrial wastewater streams, and that the limitations set by the World Health Organization (residual concentration of 70 microg/l Mo) can easily be met.

Identifying the cause of soil cadmium contamination with Monte Carlo mass balance modelling: a case study from Potosi, Bolivia.

The Chayanta river in Potosi, Bolivia is polluted by present and past mining activities in the districts of Siglo XX and Llallagua. The river water, which is enriched with cadmium (Cd), is used for irrigation in the Quila Quila and Asiruri valleys where the median soil Cd concentration is 20 mg kg(-1), well above the background value of < 0.5 mg kg(-1). The objective of this study was to predict current soil contamination using a retrospective mass balance. Monitoring data were collected on Cd concentrations in irrigation water, irrigation application rates, crop yield and composition, and soil properties including pore water composition. The mass balance was made assuming constant model parameters since the start of upstream mining operations about 85 years ago (1920). The parameter uncertainty was taken into account with a Monte Carlo analysis. The current annual Cd input by irrigation is 800 g ha(-1). The annual output of Cd through removal of the crop harvest and leaching is less than 10 g ha(-1). The predicted soil Cd concentrations after 85 years of contamination (geometric mean: 21.9 mg x kg(-1), 10th and 90th percentile 7.2-65.1 mg kg(-1) respectively) matched the distribution of observed values (geometric mean: 18.6 mg kg(-1); 10th and 90th percentile 4.7-65.9 mg kg(-1) respectively; n = 56). This study confirmed that irrigation water is the prime source of soil Cd enrichment in that area. The Monte Carlo analysis is a convenient way of including parameter uncertainty in mass balance modelling and of estimating spatial variability of the contamination.

Polymeric cracking of waste polyethylene terephthalate to chemicals and energy.

Polyethylene terephthalate (PET) is a widely used thermoplastic. PET residues represent on average 7.6 wt% of the different polymer wastes in Europe. Pyrolysis of these wastes is attracting increasing interest, and PET is a potential candidate for this thermal process. The paper measures and discusses the kinetics of the pyrolysis reaction in terms of the reaction rate constants as determined by dynamic thermogravimetric analysis, with special emphasis on the required heating rate to obtain relevant results. The product yields and compositions are also determined. Gaseous products represent 16-18 wt%. The amounts of condensables and carbonaceous residue are a function of the operating mode, with slow pyrolysis producing up to 24 wt% of carbonaceous residue. Major condensable components are benzoic acid, monovinyl terephthalate, divinyl terephthalate, vinyl benzoate, and benzene. The present paper complements previous literature findings by (1) the study of the influence of the heating rate on the reaction kinetics in dynamic pyrolysis tests, (2) the isothermal investigation in a fluidized bed reactor to pyrolyze PET, and (3) the assessment of upgrading and recovery of the products. The paper concludes with a proposed reactor recommendation for PET pyrolysis, in either the bubbling or circulating fluidized bed operating mode.

Efficiencies of available organic mixtures for the biological treatment of highly acidic-sulphate rich drainage of the San Jose mine, Bolivia.

The environmental contamination due to mining activities in the Andean region of Bolivia is a serious concern, as it leads to highly acidic (pH 2.4) acid mine drainage (AMD), severely polluted by sulfate (>12,000 mg L-1). Passive bioreactors entailing biological sulfate reduction and removal of metals through sulfide precipitation have been recognized as a promising biotechnology. The reactivity of mixtures containing locally available substrates: sheep manure, compost and straw, was assessed through batch experiments conducted with a synthetic solution simulating the composition of AMD from San José mine (Oruro). The removal of sulfate and metals was successful in all reactors, at the end of the experiment (56 days) sulfate concentrations dropped to 1378-2081 mg L-1, corresponding to a removal efficiency between 84% and 89%, while average removal for Fe, Zn, Pb, and Cd were 99.8%, 98.5%, 94.7%, 98.6%, respectively. The sulfate and metal removal showed three phases. In the first phase, the removal was independent of the organic composition and attributable to pH-controlled mechanisms i.e. adsorption, precipitation of oxy(hydroxides) and co-precipitation. During the second phase, sulfate and metals concentrations remained rather constant; while in the third phase, the removal was affected by the organic matter composition. Sulfate removal rate attained the highest values (227-243 mg L-1 d-1) in the third phase, and it was attributable to biological reduction with not sulfate limitation. The depletion of nutrients rather than the sulfate availability may have limited the sulfate removal at the end of the experiment.

Data supporting the improvement of forecasting and control of electricity consumption in hotels.

Improving and managing the electricity efficiency in hotel facilities is essential to reduce the hotel operation costs and its environmental impacts. The data presented shows the evolution of the electricity consumption and management between 2013 and 2015 in two hotel facilities in Cuba (one beach hotel and one city hotel). The data additionally includes the daily measures used to develop control tools for an energy management system. The data presented in the article relates to the research study: Tools to improve forecasting and control of the electricity consumption in hotels Cabello et al., 2016, and it corresponds to the energy audits developed in one beach hotel (Hotel A) and one city hotel (Hotel B) in Cuba.

Assessment of Pb-slag, MSWI bottom ash and boiler and fly ash for using as a fine aggregate in cement mortar.

Three types of wastes, metallurgical slag from Pb production (SLG), the sand-sized (0.1-2 mm) fraction of MSWI bottom ash from a grate furnace (SF), and boiler and fly ash from a fluidised bed incinerator (BFA), were characterized and used to replace the fine aggregate during preparation of cement mortar. The chemical and mineralogical behaviour of these wastes along with the reactivities of the wastes with lime and the hydration behaviour of ordinary Portland cement paste with and without these wastes added were evaluated by various chemical and instrumental techniques. The compressive strengths of the cement mortars containing waste as a partial substitution of fine aggregates were also assessed. Finally, leaching studies of the wastes and waste containing cement mortars were conducted. SLG addition does not show any adverse affect during the hydration of cement, or on the compressive strengths behaviours of mortars. Formation of expansive products like ettringite, aluminium hydroxide and H2 gas due to the reaction of some constituents of BFA and SF with alkali creates some cracks in the paste as well as in the cement mortars, which lower the compressive strength of the cement mortars. However, utilization of all materials in cement-based application significantly improves the leaching behaviour of the majority of the toxic elements compared to the waste as such.

Geochemical modelling of arsenic and selenium leaching in alkaline water treatment sludge from the production of non-ferrous metals.

Geochemical modelling of leaching of oxyanion forming elements such as arsenic (As) and selenium (Se) is frequently not successful. A consistent thermodynamic dataset of As and Se was therefore composed, not only including precipitation, but also adsorption and solid solution, and was applied to the pH-dependent leaching behaviour of As and Se in an alkaline residue with a pH 11.1 from the lime treatment of sulphuric acid wastewaters from the production of non-ferrous metals. The As and Se content ranged up to 6.7 wt% and 0.29 wt%, respectively and speciation analysis showed that 96.3% of As occured as arsenate whereas Se speciation comprised 79% selenate and 21.0% selenite. XRD and SEM/EDX analysis showed that arsenate occurred as rauenthalite (Ca(3)(AsO(4))(2).10H(2)O), associated with gypsum, the most important mineral. Arsenate and arsenite concentrations were only slightly below equilibrium with rauenthalite and calciumarsenite (CaHAsO(3)), respectively and consideration of adsorption and solid solution only marginally improved model predictions. Selenate (Se(VI)) and selenite (Se(IV)), on the other hand, were far from equilibrium with their corresponding calcium metalate. The application of solid solutions and adsorption of Se(VI) and Se(IV) oxyanions with gypsum, calcite and ettringite significantly improved model predictions but missing thermodynamic data and especially the lack of a comprehensive model for solid solution and surface exchange with calcite and ettringite still hampered efficient modelling.

Data supporting the assessment of biomass based electricity and reduced GHG emissions in Cuba.

Assessing the biomass based electricity potential of developing nations like Cuba can help to reduce the fossil fuels dependency and the greenhouse gas emissions. The data included in this study present the evolution of electricity production and greenhouse gas emissions in Cuba. Additionally, the potentialities to produce biomass based electricity by using the most significant biomass sources in Cuba are estimated. Furthermore, estimations of the potential reductions of greenhouse gas emissions, resulting from implementing the biomass based electricity potential of the different sources discussed in the study, are included. Results point to the most promising biomass sources for electricity generation and their potential to reduce GHG emissions.

Elevated cadmium concentrations in potato tubers due to irrigation with river water contaminated by mining in Potosí, Bolivia.

Risk of cadmium (Cd) in the human food chain in Cd-contaminated areas is often limited by phytotoxicity from zinc (Zn) that is associated with the Cd contamination. A semiarid area, 60 km downstream of a tin mine in Bolivia, was surveyed where irrigation with Cd-contaminated river water (65-240 microg Cd L(-1)) has increased median soil Cd to 20 mg kg(-1) while median soil Zn was only about 260 mg kg(-1). Cadmium concentrations in potato tubers increased from background values (0.05 mg kg(-1) dry wt.) in soils irrigated with spring water to a median value of 1.2 mg kg(-1) dry wt. in the affected area. Median concentration of Cd in soil solutions was 27 microg L(-1) and exceeded the corresponding value of Zn almost twofold. Soil-extractable chloride ranged from 40 to 1600 mg Cl(-) kg(-1) and was positively correlated with soil total Cd. Increasing soil solution Cl(-) decreased the solid-liquid distribution coefficient of Cd in soil. Soil total Cd explained 64% of the variation of tuber Cd concentration while only 3% of the variation was explained by soil extractable Cl(-) (n = 49). The estimated dietary Cd intake from potato consumption by the local population is about 100 microg d(-1) which exceeds the WHO recommended total daily intake. It is concluded that the food chain risk of Cd in the irrigation water of the semiarid area is aggravated by the association with Cl(-) and, potentially, by the relatively large Cd/Zn ratio.

Flux decline in nanofiltration due to adsorption of dissolved organic compounds: model prediction of time dependency.

Flux decline during nanofiltration of aqueous solutions containing dissolved organic compounds is mainly caused by adsorption of these compounds in the membrane pores and on the membrane surface. In this paper, flux decline is modeled by incorporating the loss of permeability due to adsorption in the Spiegler-Kedem equation. This results in a logarithmic relation between normalized flux decline and time until the adsorption equilibrium is reached and the flux reaches a constant value. In this way, the expected flux decline due to adsorption of organic compounds can be estimated. Two different parameters were used in the model: the time delay t(0), which corresponds to the time at which the adsorption process in the membrane pores and on the membrane surface sets in, and the corresponding reduction of free (pore) volume (b). Both parameters depend on the hydrophobicity of the compounds and on the feed concentration.

Experimental study and modelling of Cr (VI) removal from wastewater using Lemna minor.

The removal of Cr(VI) from wastewater by Lemna minor was studied both at laboratory and pilot scale. Laboratory tests were conducted under different conditions of initial Cr(VI) concentration (0.5 and 2.0 mg/l) and temperature (285 and 291 K). Batch experiments were carried out during 16 days in which the chromium concentrations, both in the biomass and in wastewater were measured. Data were used to characterize the biouptake capacity of the biomass; results showed that it increases with the temperature and when the initial Cr concentration decreases. The biouptake process could be fitted by an equation, with a correlation coefficient of 0.98. The removal process was assessed using the data of the variation of chromium concentration in the wastewater with respect to time; this allowed obtaining constant parameters which were applied in a mathematical model for the assessment of duckweed systems in a pilot scale plant.

Antimony leaching from uncarbonated and carbonated MSWI bottom ash.

The recycling potential of municipal solid waste incinerator (MSWI) bottom ash may be limited by the leaching of antimony (Sb). Therefore, treatment methodologies need to be developed. The pH-dependent leaching behaviour of this oxyanion-forming element in fresh and weathered bottom ash is, however, not understood. Sb leaching was investigated in a wide range of both pH and extent of carbonation. Sb came close to equilibrium with calcium antimonate (Ca[Sb(OH)(6)](2)) at acid and neutral pH. Therefore, adsorption experiments with synthetic calcite (CaCO(3)), ettringite (Ca(6)Al(2)(SO(4))(3)(OH)(12) x 26H(2)O), gypsum (CaSO(4) x 2H(2)O), and portlandite (Ca(OH)(2)) and adsorption modelling to hydrous ferric oxides (HFO) and amorphous aluminium minerals (AAM) were conducted to investigate which minerals decrease Sb leaching below equilibrium with calcium antimonate. At pH>12, calcium antimonate comes into solution due to portlandite formation, but the subsequent increase in Sb leaching is reduced due to strong interaction of Sb with portlandite and ettringite. Ettringite appears to be an important host mineral for Sb at the natural pH of mildly weathered bottom ash (11.8) because a minimum in leaching is observed. When pH is decreased below 10.5, ettringite dissolves and Sb comes into solution, approaching equilibrium with calcium antimonate near pH 9. Gypsum showed no affinity for Sb. The interaction of calcite with Sb was not clear. Adsorption modelling suggested that HFO, rather than AAM, control Sb leaching when pH<9. During carbonation, Sb leaching first increased, most likely due to dissolution of ettringite. Then, Sb leaching decreased, since the pH became low enough to allow sorption by HFO.

Immobilization of antimony in waste-to-energy bottom ash by addition of calcium and iron containing additives.

The leaching of Sb from waste-to-energy (WtE) bottom ash (BA) often exceeds the Dutch limit value of 0.32mgkg(-1) for recycling of BA in open construction applications. From the immobilization mechanisms described in the literature, it could be concluded that both Ca and Fe play an important role in the immobilization of Sb in WtE BA. Therefore, Ca and Fe containing compounds were added to the samples of the sand fraction of WtE BA, which in contrast to the granulate fraction is not recyclable to date, and the effect on the Sb leaching was studied by means of batch leaching tests. Results showed that addition of 0.5 and 2.5% CaO, 5% CaCl2, 2.5% Fe2(SO4)3 and 1% FeCl3 decreased the Sb leaching from 0.62±0.02mgkgDM(-1) to 0.20±0.02, 0.083±0.044, 0.25±0.01, 0.27±0.002 and 0.29±0.02mgkgDM(-1), respectively. Due to the increase in pH from 11.41 to 12.53 when 2.5% CaO was added, Pb and Zn leaching increased and exceeded the respective leaching limits. Addition of 5% CaCO3 had almost no effect on the Sb leaching, as evidenced by the resulting 0.53mgkgDM(-1) leaching concentration. This paper shows a complementary enhancement of the effect of Ca and Fe, by comparing the aforementioned Sb leaching results with those of WtE BA with combined addition of 2.5% CaO or 5% CaCl2 with 2.5% Fe2(SO4)3 or 1% FeCl3. These lab scale results suggest that formation of romeites with a high Ca content and formation of iron antimonate (tripuhyite) with a very low solubility are the main immobilization mechanisms of Sb in WtE BA. Besides the pure compounds and their mixtures, also addition of 10% of two Ca and Fe containing residues of the steel industry, hereafter referred to as R1 and R2, was effective in decreasing the Sb leaching from WtE BA below the Dutch limit value for reuse in open construction applications. To evaluate the long term effect of the additives, pilot plots of WtE BA with 10% of R1 and 5% and 10% of R2 were built and samples were submitted to leaching tests at regular intervals over time. The Sb leaching from untreated WtE BA was just below or above the Dutch limit value. The Sb leaching from the pilot plots of BA with additives first remained stable around 0.13mgkg(-1) but had a tendency to slightly increase after 6months, indicating the need for further research on the effect of weathering, and more specifically of carbonation, on Sb leaching from WtE BA.

Transport of pure components in pervaporation through a microporous silica membrane.

The pervaporation mechanism of pure components through a commercial microporous silica membrane was studied by performing experiments using water, methanol, ethanol, 2-propanol, and n-propanol in the 40-80 degrees C temperature range. Experimental fluxes were correlated to feed temperature and viscosity. It was found that the permeation mechanism obeys the adsorption-diffusion description, covering both the microscopic models based on configurational (micropore) diffusion and on activated surface diffusion. The contribution of convection was negligible. Size parameters for the permeating molecules such as molecular weight, kinetic diameter, and effective diameter, which are expected to have an influence on diffusion, did not correlate with the flux, thus strongly emphasizing the importance of sorption as the rate-determining step for transport in the pervaporation process. This was confirmed by correlating parameters reflecting polarity with flux: an exponential relation between the Hansen polarity (especially the hydrogen bonding component) and the flux was observed. A similar correlation was found between the dielectric constant and the flux. Furthermore, the flux increases in the same direction as the hydrophilicity of the pure components (log P). The effects of membrane surface tension and contact angles are less outspoken, but experiments performed on glass supported and silica supported membrane top layers suggest an important influence of the sublayers on the flux.

Recycling of spent adsorbents for oxyanions and heavy metal ions in the production of ceramics.

Spent adsorbents for oxyanion forming elements and heavy metals are classified as hazardous materials and they are typically treated by stabilization/solidification before landfilling. The use of lime or cement for stabilization/solidification entails a high environmental impact and landfilling costs are high. This paper shows that mixing spent adsorbents in the raw material for the production of ceramic materials is a valuable alternative to stabilize oxyanion forming elements and heavy metals. The produced ceramics can be used as construction material, avoiding the high economic and environmental impact of stabilization/solidification followed by landfilling. To study the stabilization of oxyanion forming elements and heavy metals during the production process, two series of experiments were performed. In the first series of experiments, the main pollutant, Mo was adsorbed onto iron-based adsorbents, which were then mixed with industrial sludge (3 w/w%) and heated at 1100°C for 30 min. Mo was chosen, as this element is easily adsorbed onto iron-based adsorbents and it is the element that is the most difficult to stabilize (i.e. the highest temperatures need to be reached before the concentrations in the leachate are reduced). Leaching concentration from the 97/3 sludge/adsorbent mixture before heating ranged between 85 and 154 mg/kg; after the heating process they were reduced to 0.42-1.48 mg/kg. Mo was actually stabilized, as the total Mo concentration after addition was not affected by the heat treatment. In the second series of experiments, the sludge was spiked with other heavy metals and oxyanion forming elements (Cr, Ni, Cu, Zn, As, Cd and Pb) in concentrations 5 times higher than the initial concentrations; after heat treatment the leachate concentrations were below the regulatory limit values. The incorporation of spent adsorbents in ceramic materials is a valuable and sustainable alternative to the existing treatment methods, saving raw materials in the ceramics production process and avoiding the use of stabilizing agents. Besides, spent adsorbents added to the raw material for ceramic products, may improve their aesthetic and structural properties.

Removal of pollutants from surface water and groundwater by nanofiltration: overview of possible applications in the drinking water industry.

During the last decade, nanofiltration (NF) made a breakthrough in drinking water production for the removal of pollutants. The combination of new standards for drinking water quality and the steady improvement of the nanofiltration process have led to new insights, possible applications and new projects on lab-scale, pilot scale and industrial scale. This paper offers an overview of the applications in the drinking water industry that have already been realised or that are suggested on the basis of lab-scale research. Applications can be found in the treatment of surface water as well as groundwater. The possibility of using NF for the removal of hardness, natural organic material (NOM), micropollutants such as pesticides and VOCs, viruses and bacteria, salinity, nitrates, and arsenic will be discussed. Some of these applications have proven to be reliable and can be considered as known techniques; other applications are still studied on laboratory scale. Modelling is difficult due to effects of fouling and interaction between different components. The current insight in the separation mechanisms will be briefly discussed.