Impact of COVID-19 restrictions on hourly levels of PM10, PM2.5 and black carbon at an industrial suburban site in northern Spain.

Due to the COVID-19 pandemic, lockdown restrictions were established around the world. Many studies have assessed whether these restrictions affected atmospheric pollution. Comparison between them is difficult as the periods of time considered are generally not the same and thus, different conclusions may be reached. Besides, most of them consider mean daily pollutant concentration, despite differences being observed according to the time of day. In this study, the hourly levels of PM10, PM2.5 and black carbon (BC) in an industrial suburban area in the north of Spain were analysed from May 2019 to June 2020 and compared with those from the literature, using the same period in each case. In general, the highest concentrations were reached when the wind direction came from the southwest (where a steelworks, a coal-fired power plant and other industries are located) and during the night-time, both before and during the lockdown. The highest concentrations of PM10, PM2.5 and BC were observed from December to February (on average: 45, 17 and 1.3 µg m-3, respectively). The decrease/increase in those pollutants levels during the lockdown were found to be highly dependent on the period considered. Indeed, PM10 can be found to decrease by up to 39% or increase by 12%; PM2.5 can decrease by 21% or increase by up to 36%; and BC, although it generally decreases (by up to 42%), can increase by 7.4%.

Impact of COVID-19 restrictions on the dry deposition fraction of settleable particulate matter at three industrial urban/suburban locations in northern Spain.

Ninety 24-h samples of the dry deposition fraction of settleable particulate matter (DSPM) were collected at one suburban industrial site ('EMA') and two urban industrial sites ('Lauredal' and 'Laboratory') in the western area of Gijón (North of Spain) from December 2019 to June 2020. The levels registered point to an environmental issue that should receive close attention from environmental authorities. Before lockdown restrictions due to COVID-19 were established, all samples collected at the EMA site exceeded 300 mg·m-2·d-1 (the Spanish limit value until 2002). Large amounts of DSPM were also registered at the Lauredal and Laboratory sites, maximum levels reaching 1039.2 and 672.7 mg·m-2·d-1, respectively. Seven metals were analysed in DSPM samples: Al, Ca, Fe, K, Mg, Mn and Na. Fe reached the highest values: 2473.4, 463.4 and 293.3 mg·m-2·d-1 (EMA, Lauredal and Laboratory sites, respectively). This study quantifies the reductions in the DSPM levels registered (on average, 97.2, 73.5 and 90.5% at the EMA, Lauredal and Laboratory sites, respectively) during the lockdown, which involved the restriction of population mobility and industrial activity. The influence of wind speed and its direction were also assessed to better understand the role of these restrictions in the observed reductions. The concentrations of all the metals in the DSPM were reduced by more than 75%, on average, except for K at the Laboratory and Lauredal sites. These decreases were much higher than those found by other authors for smaller fractions of the atmospheric particulate matter (PM10, PM2.5). The findings of the present study highlight the importance of DSPM in highly industrialized urban/suburban locations and indicate the direction that legal measures might take, given the influence of anthropogenic emissions.

Removal of fluoride from coke wastewater by aluminum doped chelating ion-exchange resins: a tertiary treatment.

Coke wastewater is one of the most problematic industrial wastewaters, due to its large volume and complex pollutant load. In this study, ion exchange technology was investigated with the objective of reducing the fluoride content of the effluent from a coke wastewater treatment plant (26.7 mg F-/L). Two Al-doped exchange resins with chelating aminomethyl-phosphonic acid and iminodiacetic groups were assessed: Al-doped TP260 and TP207 resins, respectively. The effect of resin dosage, varying from 5 to 25 g/L, was evaluated. F- removal was within the range 57.8-89.3% and 72.0-92.1% for Al-doped TP260 and TP207, respectively. A kinetic study based on a generalized integrated Langmuir kinetic equation fitted the experimental data (R2 > 0.98). The parameters of the said kinetics met the optimal conditions for the ion exchange process, which seemed to be more favorable with Al-doped TP260 resin than with Al-doped TP207 resin, using the same resin dosage. Furthermore, the experimental data were well described (R2 > 0.98) by Langmuir and Freundlich isotherm models, in agreement with the findings of the kinetic study: the maximum sorption capacity was obtained for the Al-doped TP260 resin.

Settleable matter in a highly industrialized area: Chemistry and health risk assessment.

Settleable particulate matter (SPM) was collected at two sampling points within an urban area highly affected by nearby industrial activities. Total deposition values up to 386 mg ·m-2·d-1 were registered, the majority of samples exceeding the limit value established in the legislation in force in Spain until 2002 (300 mg·m-2·d-1). Dry deposition values showed high variability (8.6-830.3 mg·m-2·d-1). Forty-one metals and metalloids were analysed in the dry fraction of SPM, the main being Fe and Ca (maximums: 304.4 and 68.6 mg·m-2·d-1, respectively), followed by Al, Mg, Na, K, Mn, Ti, P and Zn. Trace elements like As and Pb reached up to 7.3 and 76.3 µg·â€¯m-2·d-1, respectively. Strong correlations (r > 0.90, p-value < 0.05) between Fe and other elements (Ca, Mn and Pb) were found at both sampling sites. Scanning electron microscopy confirmed the presence of these particles rich in Fe and Ca, in addition to other components, whose morphologies pointed out to anthropogenic sources. These results combined with meteorology data suggest a common industrial source contributing to the levels of these metals. Furthermore, a human health risk study was carried out to assess the potential carcinogenic and non-carcinogenic risks of exposure to thirteen elements in these particles (Al, As, Cd, Co, Cu, Mn, Mo, Ni, Pb, Sb, Sr, V and Zn). The highest levels of risk seemed to be associated with the presence of As, Pb and Sb.

Anthropogenic and meteorological influences on PM10 metal/semi-metal concentrations: Implications for human health.

There is growing interest in investigating the human health risk associated with metals in airborne particulate matter. The objective of this paper is the health risk assessment of Al, Be, Sb, Sn, Ti and Tl in PM10 under different advections of air masses. These metals/semi-metal were studied in samples collected in an area influenced by industrial activities in northern Spain with the aim of analysing the variations in PM10 metal/semi-metal. Elemental concentrations were assessed over a period of one year in terms of air mass origin by means of back trajectories (HYSPLIT), the conditional probability function, polar plots, PM concentration roses, aerosol maps (NAAPs) and receptor modelling. The mean concentrations of Al, Be, Sb, Sn, Ti and Tl were 254, 0.02, 1.30, 1.15, 15.3 and 0.20  ng/m3, respectively, and were within the usual range for suburban stations in Europe. The highest levels were recorded during conditions of regional air mass origin, highlighting the importance of sources not far from the station. Under these circumstances, the renovation of air masses was not produced. The main sources of metals were anthropogenic, mostly related to the use of coal and coke production. In general, the cancer and non-cancer risk values obtained in this study fell within accepted precautionary criteria in all trajectory groups. However, in order to improve air quality and reduce risks to human health, the impact resulting from the joint inhalation of Al, Be, Sb, Sn, Ti and Tl should not be ignored when air masses are fundamentally of regional origin.

Suburban air quality: Human health hazard assessment of potentially toxic elements in PM10.

PM10 samples were collected at two suburban locations in northern Spain, a traffic-industrial suburban (TIS) station located in the coastal city of Gijón and an industrial suburban (IS) station in Langreo, about 25 km inland. The aerosol samples were chemically analysed to determine ambient air concentrations of As, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Se, V and Zn. The results showed that the mean levels of As, Co, Cu, Fe, Mn, Ni, Pb and Se recorded at the IS location were higher than those at the TIS station. Mean levels of Fe and Zn in PM10 were higher than all other species at both the TIS and IS sampling sites (467 and 353 ng Fe/m3 and 46 and 282 ng Zn/m3, respectively). Human exposure to these twelve potentially toxic elements through PM10 was assessed for both children and adults using the U.S.EPA method, considering three pathways: ingestion, dermal contact and inhalation. In general, the IS location presented higher non-cancer risks than the TIS site. However, at both suburban locations, cancer and non-cancer risk values were in the acceptable range for adults, some exceptions being found. Greater health risk was estimated in the case of children. For this sector of the population, ingestion, dermal contact and/or inhalation of As, Pb and Zn in PM10 may pose a health hazard owing to possible carcinogenic/non-carcinogenic effects.

Influence of the ultrasound pretreatment on anaerobic digestion of cattle manure, food waste and crude glycerine.

To increase the production of methane, when cattle manure (CM) is digested, pretreatments can be applied and/or the manure can be co-digested with other wastes. In this research work, a mixture of CM, food waste (FW) and raw glycerine (Gly) in a proportion in weight of 87% CM, 10% FW and 3% Gly was digested, (a) without pretreatment and (b) with pretreatment by ultrasound, applying a sonication energy of 1040 kJ/kg total solids. Specific methane production was 290 L CH4/kg volatile solids (VS) without pretreatment and 520 L CH4/kg VS with pretreatment. With respect to the volumetric methane production, 1.07 L CH4/Lreactor.day was produced in the first case, and in the second case, 1.98 L CH4/Lreactor.day. We can conclude that the application of ultrasound pretreatment significantly improved the production of biogas.

Enrichment factors to assess the anthropogenic influence on PM10 in Gijón (Spain).

Thirty-two chemical species were determined in PM10 sampled at a suburban site on the north coast of Spain. Enrichment factors were applied to infer their soil/non-soil origin. The geochemical ratios were calculated using two databases: soil composition from locations in the surroundings of the sampling station and the Earth's average upper-crust composition. In the present study, dissimilarities were found between the enrichment factors obtained using these two databases. Al, Ti, La and Ce were taken as the reference elements to normalise the data, reaching analogous conclusions. Bi, Cd, Cu, Sb, Se, Sn and Zn were associated with predominantly non-soil apportionments. As the relevance of soil/non-soil sources for the other analysed elements was found to be variable, they were probably of mixed origin. Furthermore, pairs of elements showed strong relationships, thus pointing to a common origin. Na-Mg and Co-Ni, with Pearson correlation coefficients above 0.9, were respectively related to marine and industrial apportionments. Enrichment factors have proved to be a useful tool to distinguish the soil/non-soil origin of chemical species present in airborne particulate matter. However, the choice of the reference database for soil composition considerably determined the accuracy of the conclusions.

Relationship between physico-chemical characteristics and potential toxicity of PM10.

PM10 was sampled at a suburban location affected by traffic and industry in the north of Spain. The samples were analysed to determine the chemical components of PM10 (organic and elemental carbon, soluble chemical species and metals). The aim of this study was to assess the toxicity of PM10 in terms of the bulk analysis and the physico-chemical properties of the particles. Total carbon, sulphates, ammonium, chlorides and nitrates were found to be the major constituents of PM10. The contribution of the last of these was found to increase significantly with PM10 concentration (Pearson coefficient correlation of 0.7, p-value < 0.001). Individual airborne particles were characterised morphologically and chemically via a combination of Scanning Electron Microscopy and Energy-Dispersive X-ray spectroscopy (SEM-EDX). The subsequent image analysis revealed C-rich particles with shapes that pointed to combustion processes. Moreover, carbonaceous particles seemed to act as vehicles for sulphur compounds and metals (S, Na, Fe, Ca, Mg, K, Al, Mn, Zn and Cu). Coarse particles were found to be mainly constituted by crustal material and marine and carbonaceous particles. Although most of the studied individual particles in PM10 samples (86.0%) had a diameter within the 0.1-2.5 µm range, 1.8% of them had sizes lower than 0.1 µm 40.2% of the total studied particles were estimated to be inhaled and deposited in the human respiratory tract; 12.3% of these particles would reach the deepest zones, thereby posing a major risk to human health.

Influence of conditioning agents and enzymic hydrolysis on the biochemical methane potential of sewage sludge.

Biochemical methane potential (BMP) tests have been carried out on sewage sludge from two wastewater treatment plants to assess the effect of additives (FeCl(3) and two cationic polyelectrolytes) used in sludge dewatering. BMP tests were also carried out on the concentrated solid phase from the enzymic hydrolysis pre-treatment (42 °C, 48 h). FeCl(3) had no significant effect on specific methane production, obtaining 242-246 LCH(4)/kgVSo. The effect of the combination of polyelectrolyte and FeCl(3) depended on the polyelectrolyte and the sludge, but generally led to an increase in specific methane production (25-40%). When enzymic hydrolysis was applied as a pre-treatment, specific methane production increased from 6.8% in the sludge containing FeCl(3) to 20% in the sludge without FeCl(3), although the increases were not statistically significant. In terms of LCH(4)/kgVS(rem), a general improvement was achieved both by means of additives and by enzymic hydrolysis. However, this improvement was only significant in the case of sludge which had undergone previous enzymic hydrolysis (62%) and in the untreated sludge containing a polyelectrolyte and FeCl(3) (24%). Cationic polyelectrolytes inhibited solid-liquid separation during enzymic hydrolysis and, although the presence of only FeCl(3) did not affect this separation, a significant decrease (32%) in LCH(4)/kgVSrem was observed.

A case study of the characteristics of municipal solid waste in Asturias (Spain): influence of season and source.

In the present research study, the weight composition, physical-chemical composition and net calorific values of unsorted municipal solid waste (MSW) generated by a population of around 1,080,000 inhabitants in a region of northern Spain were determined. The unsorted MSW was composed of 38.1% organic fraction and 42.3% combustible fraction, with paper/cardboard constituting the most important part of the latter fraction (20.6%). The high content of textiles (10.9%) is worth noting, being practically equal to the content in plastics. The unsorted fractions present an average moisture content of 28.5% and an ash content of 29.4% (dry basis). The average lower heating value (LHV) is 10,744 kJ kg(-1). Likewise, variations in regard to the season of the year and the source of the waste were taken into consideration. A new correlation is proposed for estimating the LHV as a function of the physical composition of the waste.

Tertiary treatment of landfill leachates by adsorption.

The leachates produced at the municipal solid waste (MSW) landfill of Asturias (Spain) were submitted to a biological treatment consisting of a pressurized nitrification-denitrification process followed by ultrafiltration. The effluent from this treatment plant has a high chemical oxygen demand : biochemical oxygen demand (COD : BOD( 5)) ratio (about 25 : 1). The COD values of the effluent are above the discharge limits permitted by current legislation and therefore require a final treatment. In the present study, adsorption was investigated as a possible post-treatment. Three activated carbons (Organosorb 10, Organosorb 10MB and Filtracarb CC65/1240) were selected and equilibrium and column data were obtained. The best results were obtained with Organosorb 10MB, although adsorption capacities obtained were low and equilibrium was unfavourable. Adsorption capacities ranged between 150 and 157 mg COD g(-1) for an activated carbon dosage of 1 mg L(-1) and between 13.3 and 18.4 mg COD g(-1) for a dosage of 20 mg L(-1). As regards colour, adsorption capacities ranged between 145 and 175 UPtCo g(-1) for the lower dosage and between 16 and 29 UPtCo g(-1) for the higher dosage. Removal efficiency increased with the dosage of activated carbon employed, obtaining maximum COD and colour removals of 63 and 45%, respectively, for a dosage of 20 mg L(-1) after 5 h contact time.

Anaerobic mesophilic treatment of cattle manure in an upflow anaerobic sludge blanket reactor with prior pasteurization.

Different autonomous communities located in northern Spain have large populations of dairy cattle. In the case of Asturias, the greatest concentration of dairy farms is found in the areas near the coast, where the elimination of cattle manure by means of its use as a fertilizer may lead to environmental problems. The aim of the present research work was to study the anaerobic treatment of the liquid fraction of cattle manure at mesophilic temperature using an upflow anaerobic sludge blanket (UASB) reactor combined with a settler after a pasteurization process at 70 degrees C for 2 hr. The manure used in this study came from two different farms, with 40 and 200 cows, respectively. The manure from the smaller farm was pretreated in the laboratory by filtration through a 1-mm mesh, and the manure from the other farm was pretreated on the farm by filtration through a separator screw press (0.5-mm mesh). The pasteurization process removed the pathogenic microorganisms lacking spores, such as Enterococcus, Yersinia, Pseudomonas, and coliforms, but bacterial spores are only reduced by this treatment, not removed. The combination of a UASB reactor and a settler proved to be effective for the treatment of cattle manure. In spite of the variation in the organic loading rate and total solids in the influent during the experiment, the chemical oxygen demand (COD) of the effluent from the settler remained relatively constant, obtaining reductions in the COD of approximately 85%.

Ion exchange treatment of rinse water generated in the galvanizing process.

A study was conducted of the viability of using the cationic exchange resins Amberlite IR-120 and Lewatit SP-112 to treat rinse water generated in the galvanizing process as well as acidic wastewater containing zinc (Zn) and iron (Fe). Solutions containing either 100 mg/L of Zn at pH 5.6 (rinse water) or Fe and Zn at concentrations of 320 and 200 mg/L at pH 1.5 (acidic water), respectively, were percolated through packed beds until the resins were exhausted. Breakthrough capacities obtained ranged between 1.1 and 1.5 meq metal/mL resin. The elution of metal and the regeneration of resins were performed with hydrochloric acid. The influence of the flowrate used during the loading stage was also studied, with 0.5 bed volumes/min (3.2 cm/min) found to be the optimum flowrate.

Life cycle analysis of Municipal Solid Waste management possibilities in Asturias, Spain.

Directive 1994/62 concerning packaging and packaging waste and Directive 1999/31 related to waste disposal will substantially modify the management and treatment of Municipal Solid Waste (MSW) in Europe. In this study, a life cycle analysis has been carried out of the different possibilities of managing Municipal Solid Waste in Asturias. The "Integrated Waste Management" (IWM-1) model was employed, analysing the different alternatives for collection and treatment of MSW. This model predicts overall environmental burdens of MSW management systems and includes a parallel economical model. The sources of costs in the different systems of collection and treatment of MSW were considered in the economical analysis, as well as the sources of resource gathering that may be obtained via the sale of recovered materials. What emerges from this study is the soundness of management strategies based on biological treatment technologies in comparison with thermal treatments, together with the need to increase the level of collection at source.