Wood combustion experiments were carried out in a Portuguese woodstove to determine the effects of biofuel type, ignition technique, biomass load and cleavage, as well as secondary air supply, on the ...chemical composition of particles (PM10). Two typical wood fuels in the Iberian Peninsula were tested: pine (Pinus pinaster), a softwood, and beech (Fagus sylvatica), a hardwood. PM10 samples were analysed for organic and elemental carbon (OC and EC), levoglucosan and 56 elements. Total carbon (TC) represented 54–73wt.% of the particulate mass emitted during the combustion process, regardless of wood species burned or operating condition tested. The carbonaceous component of PM10 was dominated by OC. The OC content of PM10 was higher when higher loads were fed into the combustion chamber, for both fuels. EC represented from 8 to 35wt.% of the particulate mass. OC/EC ranged from 1.1 to 6.1 (avg. 3.0±1.8) for pine combustion and from 1.1 to 3.4 (avg. 2.0±0.8) for beech combustion. The lowest OC/EC ratios for both woods were observed for ignition from the top. Levoglucosan was found in all samples, representing from 3.7 to 7.5wt.% and from 4.2 to 8.9wt.% of PM10 emitted from the combustion of pine and beech, respectively. The use of low loads of fuel generated high amounts of levoglucosan either for pine or beech. Altogether, trace elements obtained by ICP-MS and ICP-AES comprised from 0.46wt.% to 1.41wt.% and from 0.87wt.% to 2.36wt.% of the PM10 mass for pine and beech combustion, respectively. Among elements, K, Ca, Na, Mg, Fe and Al contributed to more than 75% of the total ICP-MS mass. Potassium was the major element in almost all PM10 samples.
•Chemical composition of particles from distinct operating conditions was studied.•Organic carbon contributes to more than 30% of the PM10 mass.•K, Ca, Na, Mg, Fe and Al were the dominant trace elements in smoke particles.•PM10 composition can vary greatly with operating conditions.
Despite their significant role in source apportionment analysis, studies dedicated to the identification of tracer elements of emission sources of atmospheric particulate matter based on air quality ...data are relatively scarce. The studies describing tracer elements of specific sources currently available in the literature mostly focus on emissions from traffic or large-scale combustion processes (e.g. power plants), but not on specific industrial processes. Furthermore, marker elements are not usually determined at receptor sites, but during emission. In our study, trace element concentrations in PM
10 and PM
2.5 were determined at 33 monitoring stations in Spain throughout the period 1995–2006. Industrial emissions from different forms of metallurgy (steel, stainless steel, copper, zinc), ceramic and petrochemical industries were evaluated. Results obtained at sites with no significant industrial development allowed us to define usual concentration ranges for a number of trace elements in rural and urban background environments. At industrial and traffic hotspots, average trace metal concentrations were highest, exceeding rural background levels by even one order of magnitude in the cases of Cr, Mn, Cu, Zn, As, Sn, W, V, Ni, Cs and Pb. Steel production emissions were linked to high levels of Cr, Mn, Ni, Zn, Mo, Cd, Se and Sn (and probably Pb). Copper metallurgy areas showed high levels of As, Bi, Ga and Cu. Zinc metallurgy was characterised by high levels of Zn and Cd. Glazed ceramic production areas were linked to high levels of Zn, As, Se, Zr, Cs, Tl, Li, Co and Pb. High levels of Ni and V (in association) were tracers of petrochemical plants and/or fuel-oil combustion. At one site under the influence of heavy vessel traffic these elements could be considered tracers (although not exclusively) of shipping emissions. Levels of Zn–Ba and Cu–Sb were relatively high in urban areas when compared with industrialised regions due to tyre and brake abrasion, respectively.
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•The brines in PG ponds are extremely enriched in F, Na, Cl, Ni, Cd, Mn, Cu, Zn, and U.•Brine composition is strongly seasonal and spatial dependent.•The enrichment in aged brines is ...caused by precipitation and re-dissolution processes.•Brine evaporation produces multi-layered trace-element rich precipitates.
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.
The present study seeks to estimate the impact of industrial emissions and harbour activities on total atmospheric deposition in an Atlantic coastal area in the southwest of the Iberian Peninsula. ...Three large industrial estates and a busy harbour have a notable influence on air quality in the city of Huelva and the surrounding area. The study is based on a geochemical characterization of trace elements deposited (soluble and insoluble fractions) in samples collected at a rate of 15 days/sample from June 2008 to May 2011 in three sampling sites, one in the principal industrial belt, another in the city of Huelva, and the last, 56 km outside Huelva city in an area of high ecological interest.
The industrial emissions emitted by the Huelva industrial belt exert a notable influence on atmospheric deposition. Major deposition fluxes were registered for Fe, Cu, V, Ni, P, Pb, As, Sn, Sb, Se and Bi, principally in the insoluble fraction, derived from industrial funnel emissions and from harbour activities. Metals such as Mn, Ni, Cu and Zn, and elements such as P also have a significant presence in the soluble fraction converting them into potentially bio-available nutrients for the living organism in the ocean.
A principal component analysis certifies three common emissions sources in the area: 1) a mineral factor composed mainly of elements derived from silicate minerals mixed with certain anthropogenic species (Mg, K, Sr, Na, Al, Ba, LREE, Li, Mn, HREE, Ti, Fe, Se, V, SO42−-, Ni, Ca and P); 2) an industrial factor composed of the same trace elements in the three areas (Sb, Mo, Bi, As, Pb, Sn and Cd) thus confirming the impact of the emissions from the Huelva industrial belt on remote areas; and 3) a marine factor composed of Na, Cl, Mg and SO42−.
•Metals emitted by the Huelva industrial belt affect largely to atmospheric deposition.•Fe, Cu, V, Ni, P, Pb, As, Sn, Sb and Bi registered high fluxes in the industrial belt.•Industrial source made up of Sb, Mo, Bi, As, Pb, Sn and Cd appears in remote areas.•Industrial belt provides large amounts of toxic compounds deposited in Atlantic Ocean.•Cu, Zn, Mn and Ni in dissolved phase are deposited in ocean being potentially toxic.
Average ranges of particulate matter (PM
10 and PM
2.5) concentrations and chemical composition in Spain show significant variations across the country, with current PM
10 levels at several ...industrial and traffic hotspots exceeding recommended pollution limits. Such variations and exceedances are linked to patterns of anthropogenic and natural PM emissions, climate, and reactivity/stability of particulate species. PM
10 and PM
2.5 concentrations reach 14–22
μg
PM
10
m
−3 and 8–12
μg
PM
2.5
m
−3 at most rural/regional background sites, 25–30
μg
PM
10
m
−3 and 15–20μg
PM
2.5
m
−3 at suburban sites, 30–46
μg
PM
10
m
−3 and 20–30
μg
PM
2.5
m
−3 at urban background and industrial sites, and 46–50
μg
PM
10
m
−3 and 30–35
μg
PM
2.5
m
−3 at heavy traffic hotpots. Spatial distributions show sulphate and carbon particle levels reach maxima in industrialised areas and large cities (where traffic emissions are higher), and nitrate levels increase from the Atlantic to the Mediterranean (independent of the regional NO
x
emissions). African dust outbreaks have an influence on the number of exceedances of the daily limit value, but its additional load on the mean annual PM
10 levels is only highly significant in Southern Iberia and Canary and Balearic islands. The marine aerosol contribution is near one order of magnitude higher in the Canaries compared to the other regions. Important temporal influences include PM intrusion events from Africa (more abundant in February–March and spring–summer), regional-scale pollution episodes, and weekday versus weekend activity. Higher summer insolation enhances (NH
4)
2SO
4 but depletes particulate NO
3
− (as a consequence of the thermal instability of ammonium nitrate in summer) and Cl
− (due to HCl volatilisation resulting from the interaction of gaseous HNO
3 with the marine NaCl), as well as generally increasing dry dust resuspension under a semi-arid climate. Average trace metal concentrations rise with the highest levels at industrial and traffic hotspots sites, in some cases (Ti, Cr, Mn, Cu, Zn, As, Sn, W, and Pb) exceeding rural background levels by over an order of magnitude.
This work documents for the first time the levels and composition of atmospheric particulate matter in the historic mining district of Rio Tinto (Spain) to estimate the contribution and impact of ...resuspended particles from hazardous mine waste on air quality. The resuspended mine waste dust contributes notably (32%) to the total concentrations of toxic trace metals (Bi, As, Cu, Pb, Cd, Zn and Sb) into the atmosphere, with the consequent impact on public health.
► Geochemical signature of mine waste has been recognized in respirable particles. ► By consequence, respirable particles can impact on Air Quality and human health. ► Monitoring and quantification of respirable particles from mine waste are recommended.
•The spatial distribution of NH3 levels was investigated in six major Spanish cities.•Seasonal differences in NH3 levels were not consistent among cities.•The relationship between NH3 and ...vehicles/km2, SO2, NOX and PM10 was assessed.•Urban NH3 sources: traffic, biological, solid waste and wastewater plants, industry.•Mitigation strategies on urban NH3 are important to meet limit values of PM mass.
A detailed spatial and temporal assessment of urban NH3 levels and potential emission sources was made with passive samplers in six major Spanish cities (Barcelona, Madrid, A Coruña, Huelva, Santa Cruz de Tenerife and Valencia). Measurements were conducted during two different periods (winter–autumn and spring–summer) in each city. Barcelona showed the clearest spatial pattern, with the highest concentrations in the old city centre, an area characterised by a high population density and a dense urban architecture. The variability in NH3 concentrations did not follow a common seasonal pattern across the different cities. The relationship of urban NH3 with SO2 and NOX allowed concluding on the causes responsible for the variations in NH3 levels between measurement periods observed in Barcelona, Huelva and Madrid. However, the factors governing the variations in A Coruña, Valencia and Santa Cruz de Tenerife are still not fully understood. This study identified a broad variability in NH3 concentrations at the city-scale, and it confirms that NH3 sources in Spanish urban environments are vehicular traffic, biological sources (e.g. garbage containers), wastewater treatment plants, solid waste treatment plants and industry. The importance of NH3 monitoring in urban environments relies on its role as a precursor of secondary inorganic species and therefore PMX. Further research should be addressed in order to establish criteria to develop and implement mitigation strategies for cities, and to include urban NH3 sources in the emission inventories.
We interpret here the variability of levels of carbonaceous aerosols based on a 12 yr database from 78 monitoring stations across Spain specially compiled for this article. Data did not evidence any ...spatial trends of carbonaceous aerosols across the country. Conversely, results show marked differences in average concentrations from the cleanest, most remote sites (around 1 μg m−3 of non-mineral carbon (nmC), mostly made of organic carbon (OC) with very little elemental carbon (EC), around 0.1 μg m−3; OC / EC = 12–15), to the highly polluted major cities (8–10 μg m−3 of nmC; 3–4 μg m−3 of EC; 4–5 μg m−3 of OC; OC / EC = 1–2). Thus, urban (and very specific industrial) pollution was found to markedly increase levels of carbonaceous aerosols in Spain, with much lower impact of biomass burning and of biogenic emissions. Correlations between yearly averaged OC / EC and EC concentrations adjust very well to a potential equation (OC = 3.37 EC0.326, R2 = 0.8). A similar equation is obtained when including average concentrations obtained at other European sites (OC = 3.60EC0.491, R2 = 0.7). A clear seasonal variability in OC and EC concentrations was detected. Both OC and EC concentrations were higher during winter at the traffic and urban sites, but OC increased during the warmer months at the rural sites. Hourly equivalent black carbon (EBC) concentrations at urban sites accurately depict road traffic contributions, varying with distance from road, traffic volume and density, mixing-layer height and wind speed. Weekday urban rush-hour EBC peaks are mimicked by concentrations of primary gaseous emissions from road traffic, whereas a single midday peak is characteristic of remote and rural sites. Decreasing annual trends for carbonaceous aerosols were observed between 1999 and 2011 at a large number of stations, probably reflecting the impact of the EURO4 and EURO5 standards in reducing the diesel PM emissions. This has resulted in some cases in an increasing trend for NO2 / (OC + EC) ratios as these standards have been much less effective for the abatement of NOx exhaust emissions in passenger diesel cars. This study concludes that EC, EBC, and especially nmC and OC + EC are very good candidates for new air quality standards since they cover both emission impact and health-related issues.
New functionalized porous polyimides (PPIs-NO sub(2), PPIs-NH sub(2), and PPIs-NPy) were synthesized and characterized and the PPI-NPy materials were applied as supports to obtain heterogenized ...palladium-complexes (PPI-NPy-Pd). The PPI-NPy-Pd hybrid materials have behaved as very efficient heterogeneous catalysts in the Suzuki coupling reaction in water, affording the corresponding cross-coupling products in excellent yields. Furthermore, the catalysts have shown excellent chemical and thermal stability and good recyclability. No evidence of the leaching of Pd from the catalyst during the course of reaction was observed, suggesting true heterogeneity in our catalytic systems.
Ten years ago, Spain was hit by a severe economic crisis (2009–2013), while the economy recovered in 2014. In the present study, the source changes of PM10 from pre- and post-economic crisis to ...economic recovery were investigated using receptor model (Positive Matrix Factorization: PMF). PM10 samples were collected during 2014 at six different sites in Andalusia, located in the southern Spain (1–7° W, 37–39° N). Seven source factors were identified as soil dust (17.9–34.8%), road traffic (12.2–25.9%), industrial emission (1.2–16.6%), oil combustion (0–16.1%), sea salt (5.0–15.7%), secondary nitrate (<0.05–30.4%) and secondary sulfate (4.4–15.1%). The soil dust source had the greatest influence on these six stations, followed by the road traffic source. The area was seriously affected by industrial pollution, even to the suburban and rural areas. Industry source contribution showed an increase trend from financial crisis periods to economic recovery, and the contribution in 2014 was even higher than pre-crisis level. As a result, the concentrations of heavy metals (Zn, Cu, Pb, Cr and Ni) in the atmosphere were significant increased, thus enhanced their toxicity and health risks for people. The economic recovery after the financial crisis in Spain may be at the expense of emission control targets and air pollution.
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•This work studied the particulate matter compositions and sources in Spain.•Seven source factors were identified by Positive Matrix Factorization model.•Soil dust had the greatest influence in study area, followed by road traffic source.•Industry contribution showed an increase trend from financial crisis to recovery.•Increased industry source resulted to the increases of the atmospheric heavy metals.
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