Trends of particulate matter (PM₂.₅) and chemical composition at a regional background site in the Western Mediterranean over the last nine years (2002-2010)

The time variability and long term trends of PM₂.₅ (particulate matter of diameter <2.5 μm) at various regional background (RB) sites across Europe are studied and interpreted in this work. Data on mean annual levels of PM₂.₅ measured at Montseny (MSY, North East Spain) and various RB sites in Spain and Europe are evaluated and compared, and subsequently analysed for statistically significant trends. The MSY site registered higher average PM₂.₅ levels than those measured at a selection of other RB sites across Spain, Portugal, Germany and Scandinavia by percentage compared to the mean of all the stations in these countries, but lower than those measured in Switzerland, Italy and Austria. Reductions in PM₂.₅ were observed across all stations in Spain and Europe to varying degrees (7-49%). MSY underwent a statistically significant reduction since measurements began, indicating a year-on-year gradual decrease (−3.7 μgm¯³, calculated from the final year of data compared to the mean). Similar trends were observed in other RB sites across Spain (−1.9 μgm¯³). Reductions recorded in PM₂.₅ across Europe were varied, with many experiencing gradual, year-on-year decreases (−1.8 μgm¯³). These reductions have been attributed to various causes: the introduction and implementation of pollution abatement strategies in EU member states, the effect of the current economic crisis on emissions of PM₂.₅ and the influence of meteorology observed during the winters of 2009 and 2010. In addition, the North Atlantic Oscillation (NAO), a large scale meteorological phenomenon most prevalent during winter, was observed to influence the frequency of Saharan dust intrusions across the Iberian Peninsula. Chemical composition of PM₂.₅ at MSY is characterised by high levels of organic matter (OM) and sulphate, followed by crustal material, nitrate and ammonia. Sea Spray and elemental carbon (EC) comprised a minor part of the total PM₂.₅ mass. Statistical trend analysis was performed on the various chemical components of PM₂.₅ recorded at MSY to determine which components were accountable for the decrease in PM₂.₅ concentration. It is shown that OM underwent the largest decrease over the time period with a statistically significant trend (−1.3 μgm¯³ compared to the mean), followed by sulphate (−0.8 μgm¯³), ammonium (−0.5 μgm¯³) and nitrate (−0.4 μgm¯³). Conversely, sea spray, EC and crustal a material reductions were found to be negligible

Source apportionment of fine PM and sub-micron particle number concentrations at a regional background site in the western Mediterranean: a 2.5 year study

The chemical composition and sources of ambient fine particulate matter (PM₁) over a period of 2.5 years for a regional background site in the western Mediterranean are presented in this work. Furthermore, sub-micron particle number concentrations and the sources of these particles are also presented. The mean PM₁ concentration for the measurement period was 8.9 μgm¯³, with organic matter (OM) and sulphate comprising most of the mass (3.2 and 1.5 μgm¯³ respectively). Six sources were identified in PM₁ by Positive Matrix Factorisation (PMF): secondary organic aerosol, secondary nitrate, industrial, traffic + biomass burning, fuel oil combustion and secondary sulphate. Typically anthropogenic sources displayed elevated concentrations during the week with reductions at weekends. Nitrate levels were elevated in winter and negligible in summer, whereas secondary sulphate levels underwent a contrasting seasonal evolution with highest concentrations in summer, similar to the fuel oil combustion source. The SOA source was influenced by episodes of sustained pollution as a result of anticyclonic conditions occurring during winter, giving rise to thermal inversions and the accumulation of pollutants in the mixing layer. Increased levels in summer were owing to higher biogenic emissions and regional recirculation of air masses. The industrial source decreased in August due to decreased emissions during the vacation period. Increases in the traffic + biomass burning source were recorded in January, April and October, which were attributed to the occurrence of the aforementioned pollution episodes and local biomass burning emission sources, which include agriculture and domestic heating systems. Average particle number concentrations (N₉_₈₂₅ nm) from 5/11/2010 to 01/06/2011 and from 15/10/2011 to 18/12/2011 reached 3097 cm¯³. Five emission sources of particle of sub-micron particles were determined by Principal Component Analysis (PCA); industrial + traffic + biomass burning, new particle formation + growth, secondary sulphate + fuel oil combustion, crustal material and secondary nitrate. The new particle formation + growth source dominated the particle number concentration (56% of total particle number concentration), especially for particles 100 nm) and thus did not influence the particle number concentration significantly

Recovery of ammonium by powder synthetic zeolites from wastewater effluents: optimization of the regeneration step

Nitrogen recovery and valorization is gaining interest due to the current need for nitrogen removal, so it is of great interest that ammonium-selective sorbents be evaluated. In this study, a zeolitic material synthesized from coal fly ash (Ze–Na) in sodium form as well as its modification to potassium form (Ze–K) were evaluated as sorbent materials for the recovery of ammonium from wastewater effluents. The sorption performance was assessed through three consecutive sorption-desorption cycles reporting opposite behavior in terms of ammonium sorption capacity. Decreasing in the case of Ze–Na and to slightly increase for Ze–K due to alkaline activation of zeolite surface. The maximum sorption capacities obtained were 109 ± 4 mg NH4/g and 33 ± 1 mg NH4/g for Ze–Na and Ze–K, respectively. It is important to point out that in the case of Ze–Na, the maximum sorbent capacity was obtained during the first sorption cycle whereas in the case of Ze–K, it was obtained during the last working cycle due to the alkaline regeneration. Kinetic studies showed that after every regeneration step, the sorption kinetics turn faster as alkaline desorption increased the zeolite-specific surface, thus increasing the size of porous and enhancing the diffusion through the particle. Results obtained indicate that sorption capacity decreased significantly after every working cycle using Ze–Na whereas Ze–K followed the opposite behavior despite its initial lower sorption capacity.Peer ReviewedPreprin

Element behaviour during combustion in coal-fired Orhaneli power plant, Bursa-Turkey

This study focuses on element behaviour during combustion in the Orhaneli thermal power plant (a 210 MW unit, Bursa-Turkey). A total of 51 samples, feed coals (FCs), fly ashes (FAs) and bottom ashes (BAs), which were systematically collected over an eight-week period, have been analysed for major, minor and trace elements (Al, Ca, Fe, K, Mg, Na, S, As, B, Ba, Be, Bi, Cd, Co, Cr, Cs, Cu, Ga, Ge, Hf, Hg, Li, Mn, Mo, Nb, Ni, P, Pb, Rb, Sb, Sc, Se, Sn, Sr, Ta, Th, Ti, Tl, U, V, W, Y, Zn, Zr and REEs). This study shows that FCs on an airdried basis have high moisture (av. 9%), high volatile matter (av. 33%), very high ash yield (av. 53%), relatively high sulfur content (av. 2.14%) and low gross calorific value (av. 1775 kcal/kg). Proximate analyses of combustion residues imply that BAs have higher contents of unburned carbonaceous matter than FAs. Mean values of trace element concentrations in FCs fall within the ranges of most world coals, except for Cr, Cs, Ni and U which occur in concentrations slightly higher than those determined for most of world coals. Some elements such as S, Hg, As, B, Bi, Cd, Cs, Ge, K, Pb, Rb, Sb, Se, Sn, Tl, and Zn are indicating enrichments in FAs. The remaining elements investigated in this study have no clear segregation between FAs and BAs. The mass balance calculations point to Ca content of feed coal controlling the partitioning of elements in this power plant, producing a high removal efficiency for highly volatile elements such as Hg, B and Se, and a high retention of As, Bi, Cd, Cs, Ge, Pb, Rb, Sb, Sn, Tl and Zn in FAs. However, the high enrichment in trace elements of FAs can increase the hazardous potential of this coal by-product

Simultaneous ammonium and phosphate recovery and stabilization from urban sewage sludge anaerobic digestates using reactive sorbents

The use of low-cost inorganic sorbents as a new sustainable strategy to enhance the valorization of nutrients (N-P-K), from the urban water cycle (e.g., side streams from sewage sludge anaerobic digestion), in agriculture applications is presented. The simultaneous recovery and stabilization of ammonium and phosphate by using a mixture of two reactive sorbents (Na and K zeolites and magnesium oxide) was evaluated. The nutrients stabilization process, favoured at alkaline pH values, is carried out by a) the precipitation of phosphate ions with magnesium and/or ammonium ions and b) the sorption of ammonium by Na- and K-zeolites. MgO(s) promoted the stabilization of phosphate as bobierrite (Mg3(PO4)2(s)) or struvite (MgNH4PO4(s)) depending on the applied dose. Doses with the stoichiometric molar ratio of Mg/P promote the formation of bobierrite, while molar ratios higher than 3 favour the formation of struvite. Na zeolites (NaP1-NA, NaP1-IQE) demonstrated efficiency on ammonium stabilization between 60 ± 2 (for 15 gZ/L) to 90 ± 3% (for 50 gZ/L). The ammonium recovery efficiency is limited by the zeolite sorption capacity. If the target of the fertilizing criteria should include K, then the use of a K-zeolite (e.g., 5AH-IQE) provides a good solution. The optimum pH for the precipitation of struvite and bobierrite is 9.5 and the optimum pH for ammonium removal is between 4 and 8.5. N is present in higher concentrations (up 0.7–1 g NH4+/L) when pH is ranged between 8.2 and 8.6. The ammonium recovery ratios were better than those previously reported using only magnesium oxide or even a more expensive reagent as newberrite (MgHPO4(s)). The recovery mechanisms described generate low-solubility stabilized nutrients forms that potentially can be applied as slow-release fertilizers in agriculture. Thus, the use in agriculture of blends of digested sludge with low-solubility stabilized nutrients forms will improve soils quality properties in terms of organic matter and nutrients availability.Peer ReviewedPostprint (author's final draft

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 5 M, activation temperature of 150 °C, activation time of 8 h and KOH/fly ash ratio of 2 l/kg), with a cation exchange capacity (CEC) of 160 cmol kg−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

Testing the performance of sensors for ozone pollution monitoring in a citizen science approach

Tropospheric ozone (O3) is an environmental pollutant of growing concern, especially in suburban and rural areas where the density of air quality monitoring stations is not high. In this type of areas citizen science strategies can be useful tools for awareness raising, but sensor technologies must be validated before sensor data are communicated to the public. In this work, the performance under field conditions of two custom-made types of ozone sensing devices, based on metal-oxide and electrochemical sensors, was tested. A large array of 132 metal-oxide (Sensortech MICS 2614) and 11 electrochemical (Alphasense) ozone sensors, built into 44 sensing devices, was co-located at reference stations in Italy (4 stations) and Spain (5). Mean R2 between sensor and reference data was 0.88 (0.78–0.96) and 0.89 (0.73–0.96) for Captor (metal-oxide) and Raptor (electrochemical) nodes. The metal-oxide sensors showed an upper limit (approximately 170 µg/m3) implying that these sensors may be useful to communicate mean ozone concentrations but not peak episodes. The uncertainty of the nodes was 10% between 100 and 150 µg/m3 and 20% between 150 and 200 µg/m3, for Captors, and 10% for >100 µg/m3 for Raptors. Operating both types of nodes up to 5 months did not evidence any clear influence of drifts. The use of these sensors in citizen science can be a useful tool for awareness raising. However, significant data processing efforts are required to ensure high data quality, and thus machine learning strategies are advisable. Relative uncertainties should always be reported when communicating ozone concentration data from sensing nodes.Peer ReviewedPostprint (published version

Simultaneous ammonium and phosphate recovery and stabilization from urban sewage sludge anaerobic digestates using reactive sorbents

The use of low-cost inorganic sorbents as a new sustainable strategy to enhance the valorization of nutrients (N-P-K), from the urban water cycle (e.g., side streams from sewage sludge anaerobic digestion), in agriculture applications is presented. The simultaneous recovery and stabilization of ammonium and phosphate by using a mixture of two reactive sorbents (Na and K zeolites and magnesium oxide) was evaluated. The nutrients stabilization process, favoured at alkaline pH values, is carried out by a) the precipitation of phosphate ions with magnesium and/or ammonium ions and b) the sorption of ammonium by Na- and K-zeolites. MgO(s) promoted the stabilization of phosphate as bobierrite (Mg3(PO4)2(s)) or struvite (MgNH4PO4(s)) depending on the applied dose. Doses with the stoichiometric molar ratio of Mg/P promote the formation of bobierrite, while molar ratios higher than 3 favour the formation of struvite. Na zeolites (NaP1-NA, NaP1-IQE) demonstrated efficiency on ammonium stabilization between 60±2 (for 15gZ/L) to 90±3% (for 50gZ/L). The ammonium recovery efficiency is limited by the zeolite sorption capacity. If the target of the fertilizing criteria should include K, then the use of a K-zeolite (e.g., 5AH-IQE) provides a good solution. The optimum pH for the precipitation of struvite and bobierrite is 9.5 and the optimum pH for ammonium removal is between 4 and 8.5. N is present in higher concentrations (up 0.7-1gNH4+/L) when pH is ranged between 8.2 and 8.6. The ammonium recovery ratios were better than those previously reported using only magnesium oxide or even a more expensive reagent as newberrite (MgHPO4(s)). The recovery mechanisms described generate low-solubility stabilized nutrients forms that potentially can be applied as slow-release fertilizers in agriculture. Thus, the use in agriculture of blends of digested sludge with low-solubility stabilized nutrients forms will improve soils quality properties in terms of organic matter and nutrients availability

Indoor/outdoor relationships and mass closure of quasi-ultrafine, accumulation and coarse particles in Barcelona schools

Altres ajuts: MAGRAMA/CGL2011-26574Altres ajuts: MAGRAMA/UCA2009020083The mass concentration, chemical composition and sources of quasi-ultrafine (quasi-UFP, PM0.25), accumulation (PM0.25−2.5) and coarse mode (PM2.5−10) particles were determined in indoor and outdoor air at 39 schools in Barcelona (Spain). Quasi-UFP mass concentrations measured (25.6 μgm−3 outdoors, 23.4 μgm−3 indoors) are significantly higher than those reported in other studies, and characterised by higher carbonaceous and mineral matter contents and a lower proportion of secondary inorganic ions. Results suggest that quasi-UFPs in Barcelona are affected by local sources in the schools, mainly human activity (e.g. organic material from textiles, etc., contributing 23-46% to total quasi-UFP mass) and playgrounds (in the form of mineral matter, contributing about 9% to the quasi-UFP mass). The particle size distribution patterns of toxicologically relevant metals and major aerosol components was characterised, displaying two modes for most elements and components, and one mode for inorganic salts (ammonium nitrate and sulfate)and elemental carbon (EC). Regarding metals, Ni and Cr were partitioned mainly in quasi-UFPs and could thus be of interest for epidemiological studies, given their high redox properties. Exposure of children to quasi-UFP mass and chemical species was assessed by comparing the concentrations measured at urban background and traffic areas schools. Finally, three main indoor sources across all size fractions were identified by assessing indoor / outdoor ratios (I / O) of PM species used as their tracers: human activity (organic material), cleaning products, paints and plastics (Cl− source), and a metallic mixed source (comprising combinations of Cu, Zn, Co, Cd, Pb, As, V and Cr). Our results support the need to enforce targeted legislation to determine a minimum "safe" distance between major roads and newly built schools to reduce exposure to traffic-derived metals in quasi-UFPs

Wet and dry African dust episodes over eastern Spain

The impact of the African dust on levels of atmospheric suspended particulate matter (SPM) and on wet deposition was evaluated in eastern Iberia for the period 1996-2002. An effort was made to compile both the SPM and wet episodes. To this end, the time series of levels of TSP and PM10 in Levantine air quality monitoring stations were evaluated and complemented with the computation of back trajectories, satellite images, and meteorological analysis. Wet deposition frequency was obtained from weekly collected precipitation data at a rural background station in which the African chemical signature was identified (mainly pH and Ca2+ concentrations). A number of African dust episodes (112) were identified (16 episodes per year). In 93 out of the 112 (13 episodes per year) the African dust influence caused high SPM levels. In 49 out of 112 (7 episodes per year), wet deposition was detected, and the chemistry was influenced by dust. There is a clear seasonal trend with higher frequency of dust outbreaks in May-August, with second modes in March and October. Wet events followed a different pattern, with a marked maximum in May. Except for one event, December was devoid of African air mass intrusions. On the basis of seasonal meteorological patterns affecting the Iberian Peninsula, an interpretation of the meteorological scenarios causing African dust transport over Iberia was carried out. Four scenarios were identified with a clear seasonal trend. The impact of the different dust outbreak scenarios on the levels of PM10 recorded at a rural site (Monagrega, Teruel, Spain) in the period 1996-2002 was also evaluated