OC/EC ratio observations in Europe: Re-thinking the approach for apportionment between primary and secondary organic carbon

This study explores a large set of OC and EC measurements in PM(10) and PM(2.5) aerosol samples, undertaken with a long term constant analytical methodology, to evaluate the capability of the OC/EC minimum ratio to represent the ratio between the OC and EC aerosol components resulting from fossil fuel combustion (OC(ff)/EC(ff)). The data set covers a wide geographical area in Europe, but with a particular focus upon Portugal, Spain and the United Kingdom, and includes a great variety of sites: urban (background, kerbside and tunnel), industrial, rural and remote. The highest minimum ratios were found in samples from remote and rural sites. Urban background sites have shown spatially and temporally consistent minimum ratios, of around 1.0 for PM(10) and 0.7 for PM(2.5).The consistency of results has suggested that the method could be used as a tool to derive the ratio between OC and EC from fossil fuel combustion and consequently to differentiate OC from primary and secondary sources. To explore this capability, OC and EC measurements were performed in a busy roadway tunnel in central Lisbon. The OC/EC ratio, which reflected the composition of vehicle combustion emissions, was in the range of 03-0.4. Ratios of OC/EC in roadside increment air (roadside minus urban background) in Birmingham, UK also lie within the range 03-0.4. Additional measurements were performed under heavy traffic conditions at two double kerbside sites located in the centre of Lisbon and Madrid. The OC/EC minimum ratios observed at both sites were found to be between those of the tunnel and those of urban background air, suggesting that minimum values commonly obtained for this parameter in open urban atmospheres over-predict the direct emissions of OC(ff) from road transport. Possible reasons for this discrepancy are explored. (C) 2011 Elsevier Ltd. All rights reserved.

Size-segregated chemical composition of aerosol emissions in an urban road tunnel in Portugal

An atmospheric aerosol study was performed in 2008 inside an urban road tunnel, in Lisbon, Portugal. Using a high volume impactor, the aerosol was collected into four size fractions (PM0.5, PM0.5-1, PM1-2.5 and PM2.5-10) and analysed for particle mass (PM), organic and elemental carbon (OC and EC), polycyclic aromatic hydrocarbons (PAH), soluble inorganic ions and elemental composition. Three main groups of compounds were discriminated in the tunnel aerosol: carbonaceous, soil component and vehicle mechanical wear. Measurements indicate that Cu can be a good tracer for wear emissions of road traffic. Cu levels correlate strongly with Fe, Mn, Sn and Cr, showing a highly linear constant ratio in all size ranges, suggesting a unique origin through sizes. Ratios of Cu with other elements can be used to source apportion the trace elements present in urban atmospheres, mainly on what concerns coarse aerosol particles. (C) 2013 Elsevier Ltd. All rights reserved.

Minimização de odores em contentores de resíduos sólidos

Mestrado em Engenharia Química

Exposure to volatile organic compounds in a composting plant

Some previous studies have suggested that some of the volatile organic compounds (VOCs) found in composting plants may have a toxic effect that can influence, besides surroundings populations, workers from the composting plants. Impact of waste management to the environment and workers is already recognised as an environment and occupational health concerns. Several studies regarding the VOCs and bioaerosols emissions from composting have been conducted all over Europe and also in Asia. However, in Portugal the studies developed are scarce and normally VOCs are not studied and recognized as a risk factor present in this occupational setting. Consudering this, a study was developed in a Portuguese composting plant aiming to clarify if there was VOCs presence in the workplaces.

Accounting for the dissociating properties of organic chemicals in LCIA: an uncertainty analysis applied to micropollutants in the assessment of freshwater ecotoxicity

In life cycle impact assessment (LCIA) models, the sorption of the ionic fraction of dissociating organic chemicals is not adequately modeled because conventional non-polar partitioning models are applied. Therefore, high uncertainties are expected when modeling the mobility, as well as the bioavailability for uptake by exposed biota and degradation, of dissociating organic chemicals. Alternative regressions that account for the ionized fraction of a molecule to estimate fate parameters were applied to the USEtox model. The most sensitive model parameters in the estimation of ecotoxicological characterization factors (CFs) of micropollutants were evaluated by Monte Carlo analysis in both the default USEtox model and the alternative approach. Negligible differences of CFs values and 95% confidence limits between the two approaches were estimated for direct emissions to the freshwater compartment; however the default USEtox model overestimates CFs and the 95% confidence limits of basic compounds up to three orders and four orders of magnitude, respectively, relatively to the alternative approach for emissions to the agricultural soil compartment. For three emission scenarios, LCIA results show that the default USEtox model overestimates freshwater ecotoxicity impacts for the emission scenarios to agricultural soil by one order of magnitude, and larger confidence limits were estimated, relatively to the alternative approach.

Greener Selective Cycloalkane Oxidations with Hydrogen Peroxide Catalyzed by Copper-5-(4-pyridyl)tetrazolate Metal-Organic Frameworks

Microwave assisted synthesis of the Cu(I) compound [Cu(µ4-4-ptz)]n [1, 4-ptz = 5-(4-pyridyl)tetrazolate] has been performed by employing a relatively easy method and within a shorter period of time compared to its sister compounds. The syntheses of the Cu(II) compounds [Cu3(µ3-4-ptz)4(µ2-N3)2(DMF)2]n∙(DMF)2n (2) and [Cu(µ2-4-ptz)2(H2O)2]n (3) using a similar method were reported previously by us. MOFs 1-3 revealed high catalytic activity toward oxidation of cyclic alkanes (cyclopentane, -hexane and -octane) with aqueous hydrogen peroxide, under very mild conditions (at room temperature), without any added solvent or additive. The most efficient system (2/H2O2) showed, for the oxidation of cyclohexane, a turnover number (TON) of 396 (TOF of 40 h−1), with an overall product yield (cyclohexanol and cyclohexanone) of 40% relative to the substrate. Moreover, the heterogeneous catalytic systems 1–3 allowed an easy catalyst recovery and reuse, at least for four consecutive cycles, maintaining ca. 90% of the initial high activity and concomitant high selectivity.

Sarcoplasmic reticulum calcium ATPase is inhibited by organic vanadium coordination compounds: pyridine-2,6-dicarboxylatodioxovanadium(V), BMOV, and an amavadine analogue

Inorg Chem. 2008 Jul 7;47(13):5677-84. doi: 10.1021/ic702405d

Bioremediation of diesel contaminated soils : an investigation into the effects of biosurfactant and organic matter amendments

The aim of this study was to investigate the effects of biosurfactants and organic matter amendments on the bioremediation of diesel contaminated soil. Two strains of Pseudomonas aeruginosa with the ability to produce biosurfactant were isolated from a water and soil sample in Co. Sligo. The first strain, Isolate A, produced a biosurfactant which contained four rhamnose containing compounds, when grown in proteose peptone glucose ammonium salts medium with glucose as the carbon source. Two of the components were identified as rhamnolipid 1 and 2 whilst the other two components were unidentified. The second strain, Isolate GO, when grown in similar conditions produced a biosurfactant which contained only rhamnolipid 2. The type of aeration system used had a significant effect on the abiotic removal of diesel from soil. Forced aeration at a rate of 120L 02/kg soil/ hour resulted in the greatest removal. Over a 112 day incubation period this type o f aeration resulted in the removal o f 48% o f total hexane extractable material. In relation to bioremediation of the diesel contaminated sandy soil, amending the soil with two inorganic nutrients, KH2PO4 and NÜ4N03, significantly enhanced the removal of diesel, especially the «- alkanes, when compared to an unamended control. The biosurfactant from Isolate A and a biosurfactant produced by Pseudomonas aeruginosa NCIMB 8628 (a known biosurfactant producer), when applied at a concentration of three times their critical micelle concentration, had a neutral effect on the biodégradation o f diesel contaminated sandy soil, even in the presence o f inorganic nutrients. It was deduced that the main reason for this neutral effect was because they were both readily biodegraded by the indigenous microorganisms. The most significant removal of diesel occurred when the soils were amended with two organic materials plus the inorganic nutrients. Amendment of the diesel contaminated soil with spent brewery grain (SBG) removed significantly more diesel than amendment with dried molassed sugar beet pulp (DMSBP). After a 108 day incubation period, amendment of the diesel contaminated soil with DMSBP plus inorganic nutrients and SBG plus inorganic nutrients resulted in 72 and 89% removal of diesel range organics (DRO), in comparison to 41% removal of DRO in an inorganic nutrient amended control. The first order kinetic model described the degradation of the different diesel components with high correlation and was used to calculate Vi lives. The V2 life, of the total «-alkanes in the diesel was reduced from 40 days in the control to 8.5 and 5.1 days in the presence of DMSBP and SBG, respectively. The V2 life o f the unresolved complex mixture (UCM) in the diesel contaminated soil was also significantly reduced in the presence o f the two organics. DMSBP and SBG addition reduced UCM V2 life to 86 and 43 days, respectively, compared to 153 days in the control. The component of diesel whose removal was enhanced the greatest through the organic material amendments was the isoprenoid, pristane, a compound which until recently was thought to be nonbiodegradable and was used as an inert biomarker in oil degradation studies. The V2 life of pristane was reduced from 533 days in the nutrient amended control to 49.5 and 19.5 days in DMSBP and SBG amended soils. These results indicate that the addition o f the DMSBP and SBG to diesel contaminated soil stimulated diesel biodégradation, probably by enhancing the indigenous diesel degrading microbial population to degrade diesel hydrocarbons, whilst the addition o f biosurfactants had no enhanced effect on the bioremediation process.

The Use of Passive Samplers to Reveal Industrial and Agricultural Pollution Trends in Swiss Rivers

This study shows the efficiency of passive sampling to reveal industrial and agricultural pollution trends. Two practical applications for nonpolar and polar contaminants are presented. Low-density polyethylene (LDPE) samplers were deployed for one year in the Venoge River (VD) to monitor indicator PCBs (iPCBs, IUPAC nos. 28, 52, 101, 138, 153 and 180). The results showed that the impact of PCB emissions into the river is higher in summer than in other seasons due to the low flow rate of the river during this period. P,olar organic chemical integrative samplers (POCIS) were deployed for 4 months in the Sion-Riddes canal (VS) to investigate herbicides (terbuthylazine, diuron and linuron). Desisopropylatrazine-d5 (DIA-d5) was tested as a performance reference compound (PRC) to estimate aqueous concentration. The results showed an increase of water contamination due to the studied agricultural area. The maximal contamination was observed in April and corresponds to the period of herbicide application on the crops.

Estudi de les càrregues ambientals del compostatge casolà. Simulació d'un sistema de compostatge domèstic i determinació d'emissions de gasos contaminants

Aquest treball s’enfoca cap l’anàlisi de les emissions de gasos amb un potencial impacte negatiu sobre l’entorn que es poden emetre a l’atmosfera durant el compostatge casolà com són el metà i l’òxid nitrós pel seu paper de gasos d’efecte hivernacle i l’amoníac, però sense oblidar el seguiment dels paràmetres del procés en si i la determinació de la qualitat del compost produït. Durant poc més de 6 mesos s’ha simulat un sistema de compostatge casolà tal i com podria donar‐se en un domicili particular i s’ha confirmat la seva eficàcia en la reducció en pes del residu tractat així com l’obtenció d’un producte final altament estable i d’una qualitat més que acceptable. Pel que fa a les emissions de gasos, les quantitats determinades no són menyspreables. L’experiment s’ha realitzat per triplicat. Les emissions són molt erràtiques i no s’han trobat patrons clars en la seva evolució durant el procés de compostatge més enllà d’una certa correlació entre les emissions d’amoníac i la diferència de temperatures entre l’ambient i l’interior dels compostadors. Cal destacat un elevat grau de biaix en la determinació d’emissions gasoses a petita escala, com és el cas del compostatge casolà. Finalment constatar que la generació de lixiviats en el compostatge domèstic pot ser important donat el contingut en aigua de la matèria orgànica tractada a nivell casolà i el limitat accés a material estructurant sec que es té per a compensar‐les.

Targeting aquaporin function: potent inhibition of aquaglyceroporin-3 by a gold-based compound.

Aquaporins (AQPs) are membrane channels that conduct water and small solutes such as glycerol and are involved in many physiological functions. Aquaporin-based modulator drugs are predicted to be of broad potential utility in the treatment of several diseases. Until today few AQP inhibitors have been described as suitable candidates for clinical development. Here we report on the potent inhibition of AQP3 channels by gold(III) complexes screened on human red blood cells (hRBC) and AQP3-transfected PC12 cells by a stopped-flow method. Among the various metal compounds tested, Auphen is the most active on AQP3 (IC(50) = 0.8±0.08 µM in hRBC). Interestingly, the compound poorly affects the water permeability of AQP1. The mechanism of gold inhibition is related to the ability of Au(III) to interact with sulphydryls groups of proteins such as the thiolates of cysteine residues. Additional DFT and modeling studies on possible gold compound/AQP adducts provide a tentative description of the system at a molecular level. The mapping of the periplasmic surface of an homology model of human AQP3 evidenced the thiol group of Cys40 as a likely candidate for binding to gold(III) complexes. Moreover, the investigation of non-covalent binding of Au complexes by docking approaches revealed their preferential binding to AQP3 with respect to AQP1. The high selectivity and low concentration dependent inhibitory effect of Auphen (in the nanomolar range) together with its high water solubility makes the compound a suitable drug lead for future in vivo studies. These results may present novel metal-based scaffolds for AQP drug development.

Mitigation of methane and nitrous oxide emissions from flood-irrigated rice by no incorporation of winter crop residues into the soil

Winter cover crops are sources of C and N in flooded rice production systems, but very little is known about the effect of crop residue management and quality on soil methane (CH4) and nitrous oxide (N2O) emissions. This study was conducted in pots in a greenhouse to evaluate the influence of crop residue management (incorporated into the soil or left on the soil surface) and the type of cover-crop residues (ryegrass and serradella) on CH4 and N2O emissions from a flooded Albaqualf soil cultivated with rice (Oryza sativa L.). The closed chamber technique was used for air sampling and the CH4 and N2O concentrations were analyzed by gas chromatography. Soil solution was sampled at two soil depths (2 and 20 cm), simultaneously to air sampling, and the contents of dissolved organic C (DOC), NO3-, NH4+, Mn2+, and Fe2+ were analyzed. Methane and N2O emissions from the soil where crop residues had been left on the surface were lower than from soil with incorporated residues. The type of crop residue had no effect on the CH4 emissions, while higher N2O emissions were observed from serradella (leguminous) than from ryegrass, but only when the residues were left on the soil surface. The more intense soil reduction verified in the deeper soil layer (20 cm), as evidenced by higher contents of reduced metal species (Mn2+ and Fe2+), and the close relationship between CH4 emission and the DOC contents in the deeper layer indicated that the sub-surface layer was the main CH4 source of the flooded soil with incorporated crop residues. The adoption of management strategies in which crop residues are left on the soil surface is crucial to minimize soil CH4 and N2O emissions from irrigated rice fields. In these production systems, CH4 accounts for more than 90 % of the partial global warming potential (CH4+N2O) and, thus, should be the main focus of research.

Long-term C-CO2 emissions and carbon crop residue mineralization in an oxisol under different tillage and crop rotation systems

Soil C-CO2 emissions are sensitive indicators of management system impacts on soil organic matter (SOM). The main soil C-CO2 sources at the soil-plant interface are the decomposition of crop residues, SOM turnover, and respiration of roots and soil biota. The objectives of this study were to evaluate the impacts of tillage and cropping systems on long-term soil C-CO2 emissions and their relationship with carbon (C) mineralization of crop residues. A long-term experiment was conducted in a Red Oxisol in Cruz Alta, RS, Brazil, with subtropical climate Cfa (Köppen classification), mean annual precipitation of 1,774 mm and mean annual temperature of 19.2 ºC. Treatments consisted of two tillage systems: (a) conventional tillage (CT) and (b) no tillage (NT) in combination with three cropping systems: (a) R0- monoculture system (soybean/wheat), (b) R1- winter crop rotation (soybean/wheat/soybean/black oat), and (c) R2- intensive crop rotation (soybean/ black oat/soybean/black oat + common vetch/maize/oilseed radish/wheat). The soil C-CO2 efflux was measured every 14 days for two years (48 measurements), by trapping the CO2 in an alkaline solution. The soil gravimetric moisture in the 0-0.05 m layer was determined concomitantly with the C-CO2 efflux measurements. The crop residue C mineralization was evaluated with the mesh-bag method, with sampling 14, 28, 56, 84, 112, and 140 days after the beginning of the evaluation period for C measurements. Four C conservation indexes were used to assess the relation between C-CO2 efflux and soil C stock and its compartments. The crop residue C mineralization fit an exponential model in time. For black oat, wheat and maize residues, C mineralization was higher in CT than NT, while for soybean it was similar. Soil moisture was higher in NT than CT, mainly in the second year of evaluation. There was no difference in tillage systems for annual average C-CO2 emissions, but in some individual evaluations, differences between tillage systems were noticed for C-CO2 evolution. Soil C-CO2 effluxes followed a bi-modal pattern, with peaks in October/November and February/March. The highest emission was recorded in the summer and the lowest in the winter. The C-CO2 effluxes were weakly correlated to air temperature and not correlated to soil moisture. Based on the soil C conservation indexes investigated, NT associated to intensive crop rotation was more C conserving than CT with monoculture.

Uncertainties in the prediction of spatial variability of soil CO2 emissions and related properties

The soil CO2 emission has high spatial variability because it depends strongly on soil properties. The purpose of this study was to (i) characterize the spatial variability of soil respiration and related properties, (ii) evaluate the accuracy of results of the ordinary kriging method and sequential Gaussian simulation, and (iii) evaluate the uncertainty in predicting the spatial variability of soil CO2 emission and other properties using sequential Gaussian simulations. The study was conducted in a sugarcane area, using a regular sampling grid with 141 points, where soil CO2 emission, soil temperature, air-filled pore space, soil organic matter and soil bulk density were evaluated. All variables showed spatial dependence structure. The soil CO2 emission was positively correlated with organic matter (r = 0.25, p < 0.05) and air-filled pore space (r = 0.27, p < 0.01) and negatively with soil bulk density (r = -0.41, p < 0.01). However, when the estimated spatial values were considered, the air-filled pore space was the variable mainly responsible for the spatial characteristics of soil respiration, with a correlation of 0.26 (p < 0.01). For all variables, individual simulations represented the cumulative distribution functions and variograms better than ordinary kriging and E-type estimates. The greatest uncertainties in predicting soil CO2 emission were associated with areas with the highest estimated values, which produced estimates from 0.18 to 1.85 t CO2 ha-1, according to the different scenarios considered. The knowledge of the uncertainties generated by the different scenarios can be used in inventories of greenhouse gases, to provide conservative estimates of the potential emission of these gases.

Carbon Stocks in Compartments of Soil Organic Matter 31 Years after Substitution of Native Cerrado Vegetation by Agroecosystems

ABSTRACT Changes in carbon stocks in different compartments of soil organic matter of a clayey Latossolo Vermelho Distrófico (Typic Haplustox), caused by the substitution of native savanna vegetation (cerrado sensu stricto) by agroecosystems, were assessed after 31 years of cultivation. Under native vegetation, a stock of 164.5 Mg ha-1 C was estimated in the 0.00-1.00 m layer. After 31 years of cultivation, these changes in soil C stocks were detected to a depth of 0.60 m. In the case of substitution of cerrado sensu stricto by no-tillage soybean-corn rotation, a reduction of at least 11 % of the soil C pools was observed. However, the adoption of no-tillage as an alternative to tillage with a moldboard plow (conventional system) reduced CO2 emissions by up to 12 %.