Atmospheric dust deposition on soils around an abandoned fluorite mine (Hammam Zriba, NE Tunisia).

The present study focuses on the eolian dispersion and dust deposition, of major and trace elements in soils in a semi-arid climate, around an old fluorite (CaF2) and barite (BaSO4) mine, located in Hammam Zriba in Northern Tunisia. Ore deposits from this site contain a high amount of metal sulphides constituting heavy metal pollution in the surrounding environment. Samples of waste from the surface of mine tailings and agricultural topsoil samples in the vicinity of the mine were collected. The soil samples and a control sample from unpolluted area, were taken in the direction of prevailing northwest and west winds. Chemical analysis of these solids was performed using both X-ray fluorescence and X-ray diffraction. To determine the transfer from mine wastes to the soils, soluble fraction was performed by inductively coupled plasma and ionic chromatography. The fine grained size fraction of the un-restored tailings, still contained significant levels of barium, strontium, sulphur, fluorine, zinc and lead with mean percentages (wt%) of 30 (calculated as BaO), 13 (as SrO), 10 (as SO3), 4 (F), 2 (Zn) and 1.2 (Pb). Also, high concentrations of cadmium (Cd), arsenic (As) and mercury (Hg) were found with an averages of 36, 24 and 1.2mgkg-1, respectively. As a result of the eolian erosion of the tailings and their subsequent wind transport, the concentrations of Ba, Sr, S, F, Zn and Pb were extremely high in the soils near to the tailings dumps, with 5%, 4%, 7%, 1%, 0.8% and 0.2%, respectively. Concentration of major pollutants decreases with distance, but they were high even in the farthest samples. Same spatial distribution was observed for Cd, As and Hg. While, the other elements follow different spatial patterns. The leaching test revealed that most elements in the mining wastes, except for the anions, had a low solubility despite their high bulk concentrations. According the 2003/33/CE Decision Threshold, some of these tailings samples were considered as hazardous. Furthermore, other waste samples, considered non hazardous, were not inert. In contrast, the SO42-, Ba, Pb and Sb leachable contents measured in most of the soil samples were relatively high, exceeding the inert threshold for landfill disposal of wastes.

Speciation, behaviour, and fate of mercury under oxy-fuel combustion conditions.

The work presented here reports the first study in which the speciation, behaviour and fate of mercury (Hg) have been evaluated under oxy-fuel combustion at the largest oxy-Pulverised Coal Combustion (oxy-PCC) demonstration plant to date during routine operating conditions and partial exhaust flue gas re-circulation to the boiler. The effect of the CO2-rich flue gas re-circulation on Hg has also been evaluated. Results reveal that oxy-PCC operational conditions play a significant role on Hg partitioning and fate because of the continuous CO2-rich flue gas re-circulations to the boiler. Mercury escapes from the cyclone in a gaseous form as Hg(2+) (68%) and it is the prevalent form in the CO2-rich exhaust flue gas (99%) with lower proportions of Hg(0) (1.3%). The overall retention rate for gaseous Hg is around 12%; Hg(0) is more prone to be retained (95%) while Hg(2+) shows a negative efficiency capture for the whole installation. The negative Hg(2+) capture efficiencies are due to the continuous CO2-rich exhaust flue gas recirculation to the boiler with enhanced Hg contents. Calculations revealed that 44mg of Hg were re-circulated to the boiler as a result of 2183 re-circulations of CO2-rich flue gas. Especial attention must be paid to the role of the CO2-rich exhaust flue gas re-circulation to the boiler on the Hg enrichment in Fly Ashes (FAs).

Potential of Hazardous Waste Encapsulation in Concrete Compound Combination with Coal Ash and Quarry Fine Additives.

Coal power plants are producing huge amounts of coal ash that may be applied to a variety of secondary uses. Class F fly ash may act as an excellent scrubber and fixation reagent for highly acidic wastes, which might also contain several toxic trace elements. This paper evaluates the potential of using Class F fly ashes (<20% CaO), in combination with excessive fines from the limestone quarry industry as a fixation reagent. The analysis included leaching experiments (EN12457-2) and several analytical techniques (ICP, SEM, XRD, etc.), which were used in order to investigate the fixation procedure. The fine sludge is used as a partial substitute in concrete that can be used in civil engineering projects, as it an environmentally safe product.

Distinctive effects of graphene oxide and reduced graphene oxide on methane production kinetics and pharmaceuticals removal in anaerobic reactors.

Graphene oxide (GO) addition to anaerobic digestion has been suggested to enhance direct electron transfer. The impact of GO (0.075 g GO g-1 VS) and biologically and hydrothermally reduced GO (bio-rGO and h-rGO, respectively) on the methane production kinetics and removal of 12 pharmaceuticals was assessed in Fed-batch reactors. A decrease of 15 % in methane production was observed in the tests with GO addition compared with the control and the h-rGO. However, bio-rGO and h-rGO substantially increased the methane production rate compared to the control tests (+40 %), in the third fed-batch test. Removal of pharmaceuticals was enhanced only during the bio-reduction of GO (1st fed-batch test), whereas once the GO was bio-reduced, it followed a similar trend in the control and h-rGO tests. The addition of GO can enhance the methane production rate and, therefore, reduce the anaerobic treatment time.

Graphene oxide addition to anaerobic digestion of waste activated sludge: Impact on methane production and removal of emerging contaminants.

The effect of graphene oxide on the anaerobic digestion of waste activated sludge was investigated at two graphene oxide concentrations (0.025 and 0.075 g graphene oxide per g volatile solids) using biochemical methane potential tests. The occurrence of 36 pharmaceuticals was monitored in the solid and liquid phases before and after the anaerobic treatment. The addition of graphene oxide improved the removal of most pharmaceuticals detected, even those that are considered persistent to biological degradation, such as azithromycin, carbamazepine, and diclofenac. No significant differences were observed in the final specific methane production without graphene oxide and with the lowest graphene oxide concentration, yet the highest graphene oxide concentration partially inhibited methane production. The relative abundance of antibiotic resistance genes was not affected by the graphene oxide addition. Finally, significant changes in the microbial community including bacteria and archaea were detected with graphene oxide addition.

Impact of graphene oxide addition on pharmaceuticals removal in anaerobic membrane bioreactor.

The addition of conductive materials to the anaerobic digestion bioreactor was suggested to enhance microbial activity. In the present work, an anaerobic membrane bioreactor treating municipal wastewater was operated for 385 days. The impact of different graphene oxide concentrations on the removal target pharmaceuticals and microbial community dynamics was investigated. The addition of graphene oxide did not impact the reactor stability, whereas the removals of antibiotics (e.g., trimethoprim and metronidazole) were enhanced. A shift in the microbial community was detected after the addition of 50-900 mg L-1 of graphene oxide, with the proliferation hydrogenotrophic methanogens. The proliferation of syntrophic microorganisms may indicate interactions via direct interspecific electron transfer. The obtained results suggest that the addition of graphene oxide at low mg L-1 concentrations to an anaerobic membrane bioreactor may be considered to improve the removal of antibiotics from municipal wastewater.

Unusual speciation and retention of Hg at a coal-fired power plant.

An unusual and different speciation of Hg in the outgoing gaseous stream of the flue gas desulfurization (OUT-FGD) system was revealed at two Spanish power plants (PP1 and PP2) equipped with a forced oxidation wet FGD system with water recirculation to the scrubber. At PP1 and PP2, a high proportion of Hg escapes from the electrostatic precipitator in gaseous form, Hg(2+) (75-86%) being the species that enters the FGD. At PP1 Hg(0) (71%) was the prevalent Hg OUT-FGD species, whereas at PP2 Hg(2+) was the prevalent Hg OUT-FGD species in 2007 (66%) and 2008 (87%). The unusual speciation of gaseous Hg OUT-FGD and the different Hg retentions between 2007 and 2008 at PP2 were attributable to the evaporation of HgCl(2) particles from the aqueous phase of gypsum slurry in the OUT-FGD gas and the Al additive used at PP2, respectively. The Al additive induced the retention of Hg as HgS in the 2007 FGD gypsum, thus reducing gaseous emissions of Hg in the OUT-FGD gas.

Study of boron behaviour in two Spanish coal combustion power plants.

A full-scale field study was carried out at two Spanish coal-fired power plants equipped with electrostatic precipitator (ESP) and wet flue gas desulfurisation (FGD) systems to investigate the distribution of boron in coals, solid by-products, wastewater streams and flue gases. The results were obtained from the simultaneous sampling of solid, liquid and gaseous streams and their subsequent analysis in two different laboratories for purposes of comparison. Although the final aim of this study was to evaluate the partitioning of boron in a (co-)combustion power plant, special attention was paid to the analytical procedure for boron determination. A sample preparation procedure was optimised for coal and combustion by-products to overcome some specific shortcomings of the currently used acid digestion methods. In addition boron mass balances and removal efficiencies in ESP and FGD devices were calculated. Mass balance closures between 83 and 149% were obtained. During coal combustion, 95% of the incoming boron was collected in the fly ashes. The use of petroleum coke as co-combustible produced a decrease in the removal efficiency of the ESP (87%). Nevertheless, more than 90% of the remaining gaseous boron was eliminated via the FGD in the wastewater discharged from the scrubber, thereby causing environmental problems.

Phosphate recovery from aqueous solution by K-zeolite synthesized from fly ash for subsequent valorisation as slow release fertilizer.

The sorption of phosphate by K-zeolites synthesized from fly ash (FA) by hydrothermal conversion is investigated in this study. The aim is the synthesis of Ca bearing K-zeolites to recover phosphate from urban and industrial wastewater effluents. The loaded zeolites are considered as a by-products rich in essential nutrients such K and P (KP1) with a potential use as slow release fertilizer. A number of synthesis conditions (temperature, KOH-solution/FA ratio, KOH concentration, and activation time) were applied on two FA samples (FA-TE and FA-LB) with similar glass content but different content of crystalline phases, to optimize the synthesis of a zeolitic sorbent suitable for the subsequent phosphate uptake. Merlinoite and W rich zeolitic products synthesized from FA-LB and FA-TE were found to have sorption properties for phosphate removal. A maximum phosphate sorption capacity of 250 mgP-PO4/g and 142 mgP-PO4/g for the zeolitic products selected (KP1-LB and KP1-TE, respectively) was achieved. The dominant phosphate sorption mechanism, in the pH range (6-9) of treated wastewater effluents, indicated that sorption proceeds via a diffusion-controlled process involving phosphate ions coupled with calcium supply dissolution from K-zeolitic products and subsequent formation of brushite (CaHPO4 2H2O(s)). The phosphate loaded sorbent containing a relatively soluble phosphate mineral is appropriate for its use as a synthetic slow release fertilizer. The simultaneous valorisation of fly ash waste and the P recovery from treated wastewaters effluents, (a nutrient with scarce natural resources and low supply) by obtaining a product with high potential for land restoration and agriculture will contribute to develop one example of circularity.

The geochemical evolution of brines from phosphogypsum deposits in Huelva (SW Spain) and its environmental implications.

The present study focuses on the geochemistry of large phosphogypsum deposits in Huelva (SW Spain). Phosphogypsum slurry waste from fertiliser production was disposed in large ponds containing aqueous waste (i.e. brines) and exposed to weathering. These evaporation ponds were found to be dynamic environments far from attaining steady state conditions where a number of trace pollutants are subjected to temporal variations in response to changing environmental conditions. Chemical, mineralogical and morphological data were used to improve our understanding on the dynamics of a large number of elements in the phosphogypsum-brine-evaporation deposits system. Weekly sampling of brines over the course of 1 yr indicated a substantial enrichment in potentially harmful elements (e.g. As, Cr, Cu, F, Ni, U, V, Zn) present in time-dependent concentrations. The evaporation deposits formed multi-layered precipitates of chlorides, sulphates, phosphates and fluorides containing a large number of pollutants in readily soluble forms. The precipitation sequence revealed a time-dependent composition reflecting alternating precipitation and re-dissolution processes associated with seasonal changes in the local weather conditions. Concatenation of precipitation/re-dissolution stages was found to progressively enrich the brines in pollutants. These findings were supported by the observations from a tank experiment simulating the phosphogypsum-brine-evaporation deposits system under laboratory conditions. Given the substantially high concentrations of pollutants present in mobile forms in the brine-salt system, actions to abate these compounds should be implemented.

Mineralogical, chemical and leaching characteristics of ashes from residential biomass combustion.

Four types of pellets and three agro-fuels were chemically characterised and burned in a pellet stove. To assess the influence of the material composing the firebox and the combustion efficiency of distinct biomass heating devices in the composition of the bottom ashes, three of the pellets were also burned in a conventional woodstove and in a fireplace. Ashes were analysed for their C, H and N contents by an elemental analyser, whilst major and trace elements were quantified by inductively coupled plasma atomic-emission spectrometry and inductively coupled plasma mass spectrometry, respectively. The mineralogy of ashes was determined by X-ray powder diffraction. The European standard test was applied to samples to determine the leaching potential of major, minor and trace elements. The contents of major and trace elements in the different types of biomass presented enormous variations, which are reflected in dissimilar mineralogical and chemical compositions of the respective ashes. The leachable potential of several elements of environmental concern present in oxy-anionic form at the alkaline pH of biomass ashes were generally high in all samples. Concentrations of some elements in the leachates were in the range of values with classification of "hazardous materials" by the European legislation in what respects the acceptance of these wastes at landfills. Pellets made up of wood wastes and containing preservatives (chromated copper arsenate and ammoniacal copper arsenate) are of concern. Due to lower combustion efficiencies, the leachable potential for most of the trace elements in ashes from the woodstove, and especially from the fireplace, was lower than that of the pellet stove.

Physico-chemical characterization of playground sand dust, inhalable and bioaccessible fractions.

Dust is a mixture of natural and anthropogenic particles originated from multiple sources, which can represent an hazard for human health. Playgrounds are a site of particularly concern, due to sand dust ingestion by toddlers and inhalation. In this study, 37 sands used in public playgrounds in the city of Barcelona were physico-chemically characterized also in relation to routine maintenance activities such as disinfection and sand renewal. The analyzed sands show a felsic mineralogy dominated by Na-feldspar, quartz, and, to a lesser extent, K-feldspar, with minor amounts of clay minerals, carbonates and hematite. Particle fractions below 10, 2.5 and 1 µm represent, on average, 0.65%, 0.17% and 0.07% of bulk volume, respectively, although, due to the human grinding, these initial fractions increased every year by a 18%, 5% and 2% respectively. Disinfection of sands effectively reduced only the NH4+ concentration, among inorganic species. The average metal content was anthropogenically enriched, with respect to the upper continental crust, only for Sb and As. Both elements show high spatial variation indicating local sources such as road traffic for Sb (contributing mostly to the total concentration), and industry for As (also contributing with highly bioaccessible Sb, Cu and Zn). A clear inverse relationship between total concentrations of some elements and their leachable (Sb) and bioaccessible (Sb and Cr) fractions is observed. The most bioaccessible elements were Ca > Ni > Cu > Sr > Cd > Pb, all above the 25% of the total concentration. Bioaccessibility was higher for the carbonate-bearing particles and for the anthropic emitted metals (>50% of Ba, Cu, K, Pb and Zn).

Recovery of gallium and vanadium from gasification fly ash.

The Puertollano Integrated Coal Gasification Combined Cycle (IGCC) Power Plant (Spain) fly ash is characterized by a relatively high content of Ga and V, which occurs mainly as Ga2O3 and as Ga3+ and V3+ substituting for Al3+ in the Al-Si fly ash glass matrix. Investigations focused on evaluating the potential recovery of Ga and V from these fly ashes. Several NaOH based extraction tests were performed on the IGCC fly ash, at different temperatures, NaOH/fly ash (NaOH/FA) ratios, NaOH concentrations and extraction times. The optimal Ga extraction conditions was determined as 25 degrees C, NaOH 0.7-1 M, NaOH/FA ratio of 5 L/kg and 6 h, attaining Ga extraction yields of 60-86%, equivalent to 197-275 mg of Ga/kg of fly ash. Re-circulation of leachates increased initial Ga concentrations (25-38 mg/L) to 188-215 mg/L, while reducing both content of impurities and NaOH consumption. Carbonation of concentrated Ga leachate demonstrated that 99% of the bulk Ga content in the leachate precipitates at pH 7.4. At pH 10.5 significant proportions of impurities, mainly Al (91%), co-precipitate while >98% of the bulk Ga remains in solution. A second carbonation of the remaining solution (at pH 7.5) recovers the 98.8% of the bulk Ga. Re-dissolution (at pH 0) of the precipitate increases Ga purity from 7 to 30%, this being a suitable Ga end product for further purification by electrolysis. This method produces higher recovery efficiency than currently applied for Ga on an industrial scale. In contrast, low V extraction yields (<64%) were obtained even when using extreme alkaline extraction conditions, which given the current marked price of this element, limits considerably the feasibility of V recovery from IGCC fly ash.

Synthesis of merlinoite from Chinese coal fly ashes and its potential utilization as slow release K-fertilizer.

This study focuses on the synthesis of merlinoite from Chinese coal fly ashes by KOH direct conversion method, with special emphasis on the application of synthetic merlinoite as fertilizer. These fly ashes were collected from two pulverized-coal combustion (PCC) power plants in Xinjiang, Northwest China. The synthesis results are influenced by fly ash characteristics and different synthesis conditions (KOH solution concentrations, activation temperature, time, and KOH/fly ash ratios). A high quality merlinoite-rich product was synthesized under optimal activation conditions (KOH concentration of 5M, activation temperature of 150°C, activation time of 8h and KOH/fly ash ratio of 2l/kg), with a cation exchange capacity (CEC) of 160cmolkg(-1). The synthetic merlinoite is proved to be an efficient slow release K-fertilizer for plant growth, indicating that it can be widely used for high-nutrient demanding crops growing in nutrient-limited soils and for large-area poor soil amendment in opencast coal mine areas around the power plants that will substantially grow with the increasing coal combustion in Xinjiang in the near future.

Distribution of trace elements in particle size fractions for contaminated soils by a copper smelting from different zones of the Puchuncaví Valley (Chile).

Metal contents in soil samples are commonly used to evaluate contamination levels. However, the distribution of metals is dependent on particle size. We investigated the distribution of metals in various particle size fractions of the soil from four sites of the Puchuncaví Valley (Central Chile). The soil samples were segregated into size fractions ranging from 0.3 to 20µm and analyzed using inductively coupled plasma atomic emission spectrometry (ICP-AES) and inductively coupled plasma mass spectrometry (ICP-MS). The results of the statistical analysis of the total metal concentrations indicated that the soil samples from Greda and Maitenes, the sites nearest the industrial sources, are the most contaminated. For these sites, the size-fractionated samples containing higher concentrations of Cu, Zn, As, and Pb were found in the finer fractions, suggesting anthropogenic depositions from smelter facilities. In addition, a high Ca concentration was observed in the finer fractions, which could be attributed to the technological approaches used to reduce the SO2 emissions from the roasting process of copper sulfide. The mineral composition of fine particles permitted the identification of Tenorite and Calcium oxide, which are most likely associated with smelting activities, confirming emission of enriched particulate matter from the copper smelter.

Fly ash from a Mexican mineral coal I: Mineralogical and chemical characterization.

The properties of coal fly ash are strongly dependent on the geological origin and the combustion process of the coal. It is important to characterize regional fly ash in detail to ascertain its potential uses as raw material in the production of high value products. The physicochemical properties of fly ash coming from the "Jose Lopez Portillo" coal-fired power plant, Coahuila, Mexico (MFA), are presented in this work. A detailed study of trace elements, the chemical composition of the amorphous phase, thermal stability and the leaching of contaminant elements under different conditions are included. MFA is composed of mullite, quartz, calcite, magnetite and an amorphous phase. This material contains mainly silica (59.6%), alumina (22.8%) and magnetite (5.6%). Its amorphous phase (78.3%) has a high silica (49.4%) and alumina (14.4%) content. According to its mineralogical and chemical composition, MFA is potentially useful as a raw material for making cement, silica, and alumina, as well as low silica/alumina ratio zeolites. Deleterious elements could be removed during the zeolitization process or with an additional acid treatment. Because of its morphological properties and structural and thermal stability, MFA can be used in thermal isolation and refractory materials and as a support for heterogeneous catalysts.

Germanium recovery from gasification fly ash: evaluation of end-products obtained by precipitation methods.

In this study the purity of the germanium end-products obtained by two different precipitation methods carried out on germanium-bearing solutions was evaluated as a last step of a hydrometallurgy process for the recovery of this valuable element from the Puertollano Integrated Gasification Combined Cycle (IGCC) fly ash. Since H(2)S is produced as a by-product in the gas cleaning system of the Puertollano IGCC plant, precipitation of germanium as GeS(2) was tested by sulfiding the Ge-bearing solutions. The technological and hazardous issues that surround H(2)S handling conducted to investigate a novel precipitation procedure: precipitation as an organic complex by adding 1,2-dihydroxy benzene pyrocatechol (CAT) and cetyltrimethylammonium bromide (CTAB) to the Ge-bearing solutions. Relatively high purity Ge end-products (90 and 93% hexagonal-GeO(2) purity, respectively) were obtained by precipitating Ge from enriched solutions, as GeS(2) sulfiding the solutions with H(2)S, or as organic complex with CAT/CTAB mixtures and subsequent roasting of the precipitates. Both methods showed high efficiency (>99%) to precipitate selectively Ge using a single precipitation stage from germanium-bearing solutions.

Influence of a modification of the petcoke/coal ratio on the leachability of fly ash and slag produced from a large PCC power plant.

Co-firing of coal with inexpensive secondary fuels such as petroleum coke is expected to increase in the near future in the EU given that it may provide certain economic and environmental benefits with respect to coal combustion. However, changes in the feed fuel composition of power plants may modify the bulk content and the speciation of a number of elements in fly ash and slag. Consequently, leachability of these byproducts also can be modified. This study is focused on identifying the changes in the environmental quality of co-fired fly ash and slag induced by a modification of the petcoke/coal ratio. Petcoke was found to increase the leachable content of V and Mo and to enhance the mobility of S and As. However, with the exception of these elements, the addition of this secondary fuel did not drastically modify the bulk composition or the overall leachability of the resulting fly ash and slag.