Acid-base properties of humic substances from composted and thermally-dried sewage sludges and amended soils as determined by potentiometric titration and the NICA-Donnan model

The acid-base properties of humic acids (HAs) and fulvic acids (FAs) isolated from composted sewage sludge (CS), thermally-dried sewage sludge (TS), soils amended with either CS or TS at a rate of 80 t ha(-1)y(-1) for 3y and the corresponding unamended soil were investigated by use of potentiometric titrations. The non-ideal competitive adsorption (NICA)-Donnan model for a bimodal distribution of proton binding sites was fitted to titration data by use of a least-squares minimization method. The main fitting parameters of the NICA-Donnan model obtained for each HA and FA sample included site densities, median affinity constants and widths of affinity distributions for proton binding to low and high affinity sites, which were assumed to be, respectively, carboxylic- and phenolic-type groups. With respect to unamended soil HA and FA, the HAs and FAs from CS, and especially TS, were characterized by smaller acidic functional group contents, larger proton binding affinities of both carboxylic- and phenolic-type groups, and smaller heterogeneity of carboxylic and phenolic-type groups. Amendment with CS or TS led to a decrease of acidic functional group contents and a slight increase of proton binding affinities of carboxylic- and phenolic-type groups of soil HAs and FAs. These effects were more evident in the HA and FA fractions from CS-amended soil than in those from TS-amended soil.     

Structure of Mn-Zr mixed oxides catalysts and their catalytic performance in the gas-phase oxidation of chlorocarbons

The catalytic activity and selectivity of manganese zirconia mixed oxides were evaluated for the oxidation of two common chlorinated pollutants found in waste streams, namely 1,2-dichloroethane (DCE) and trichloroethylene (TCE). Mixed oxides with varying Mn-Zr content were prepared by coprecipitation via nitrates, and subsequent calcination at 600 degrees C for 4 h in air. These catalysts were characterised by means of several techniques such as atomic emission spectrometry, N2 adsorption-desorption, powder X-ray diffraction, temperature-programmed desorption of ammonia, pyridine adsorption followed by diffuse reflectance infrared spectroscopy and temperature-programmed reduction with hydrogen. The active catalytic behaviour of Mn-Zr mixed oxides was ascribed to a substantial surface acidity combined with readily accessible active oxygen species. Hence, the mixed oxide with 40 mol% manganese content was found to be an optimum catalyst for the combustion of both chlorocarbons with a T50 value around 305 and 315 degrees C for DCE and TCE oxidation, respectively. The major oxidation products were carbon dioxide, hydrogen chloride and chlorine. It was observed that the formation of both CO2 and Cl2 was promoted with Mn loading.     

Biodegradation of heavy crude oil Maya using spent compost and sugar cane bagasse wastes

Experiments were carried out to evaluate the use of some agroindustrial wastes as supports in solid state cultures for the biodegradation of crude oil Maya in static column reactors over 15-20 days periods. Spent compost and cane bagasse wastes showed superior qualities over peat moss waste as support candidates with the advantage that they contain appreciable densities of autochthonous microorganisms in the order of 10(2) cfu g(-1). Mercuric chloride (2%) was able to completely inhibit growth of these microfloras. Biodegradation was enhanced in the presence of the IMP consortium and highest when microflora from cane bagasse only was the bioaugmentation partner (180.7 mg kg(-1) day(-1)). Combination of these waste materials (3:1 ratio, respectively) was observed to significantly biodegrade the crude oil by approximately 40% in 15 days from an initial concentration of 10,000 mg kg(-1) with a four order of magnitude increase in microbial density during this period. Spent compost and cane bagasse wastes are veritable solid support candidates for use in the biodegradation of crude oil polluted systems.     

Determination of selenium by GFAAS in slurries of fish feces to estimate the bioavailability of this micronutrient in feed used in pisciculture

This paper presents a simple, fast and sensitive method to determine selenium in samples of feces and of fish feed by graphite furnace atomic absorption spectrometry (GFAAS) through the direct introduction of slurries of the samples into the spectrometer's graphite tube. The limits of detection (LOD) and quantification (LOQ) calculated for 20 readings of the blank of the standard slurries (0.50% m/v of feces or feed devoid of selenium) were 0.31 microg l(-1) and 1.03 microg l(-1), respectively, for the standard feces slurries and 0.35 microg l(-1) and 1.16 microg l(-1), respectively, for the standard feed slurries. The proposed method was applied in studies of bioavailability of selenium in different fish feeds and the results proved consistent with that obtained from samples mineralized by acid digestion using the microwave oven.     

Larval outbreaks in West Greenland: Instant and subsequent effects on tundra ecosystem productivity and CO<Subscript>2</Subscript> exchange

Insect outbreaks can have important consequences for tundra ecosystems. In this study, we synthesise available information on outbreaks of larvae of the noctuid moth Eurois occulta in Greenland. Based on an extensive dataset from a monitoring programme in Kobbefjord, West Greenland, we demonstrate effects of a larval outbreak in 2011 on vegetation productivity and CO₂ exchange. We estimate a decreased carbon (C) sink strength in the order of 118–143 g C m^?2, corresponding to 1210–1470 tonnes C at the Kobbefjord catchment scale. The decreased C sink was, however, counteracted the following years by increased primary production, probably facilitated by the larval outbreak increasing nutrient turnover rates. Furthermore, we demonstrate for the first time in tundra ecosystems, the potential for using remote sensing to detect and map insect outbreak events.     

Riparian rehabilitation planning in an urban–rural gradient: Integrating social needs and ecological conditions

In the present context of global change and search for sustainability, we detected a gap between restoration and society: local communities are usually only considered as threats or disturbances when planning for restoration. To bridge this gap, we propose a landscape design framework for planning riparian rehabilitation in an urban–rural gradient. A spatial multi-criteria analysis was used to assess the priority of riversides by considering two rehabilitation objectives simultaneously—socio-environmental and ecological—and two sets of criteria were designed according to these objectives. The assessment made it possible to identify 17 priority sites for riparian rehabilitation that were associated with different conditions along the gradient. The double goal setting enabled a dual consideration of citizens, both as beneficiaries and potential impacts to rehabilitation, and the criteria selected incorporated the multi-dimensional nature of the environment. This approach can potentially be adapted and implemented in any other anthropic–natural interface throughout the world.     

Influence of boundary conditions on CMAQ simulations over the Iberian Peninsula

The influence of chemical boundary conditions (BC) on the response of the Community Multiscale Air Quality (CMAQ) model over the Iberian Peninsula was investigated in this study. Three strategies to supply boundary conditions in the context of the Integrated Assessment Modelling System for the Iberian Peninsula (SIMCA) were tested. Alternative methods consist in providing BC from (1) fixed, time-independent, concentration profiles, (2) concentrations predicted in a CMAQ mother domain (48 km, 1 h resolution) and (3) concentration values from the GEOS-Chem chemical-transport global model (2 × 2.5°, 3 h resolution). High resolution (3 km) simulated concentrations of the main pollutants (NO₂, NO, SO₂, O₃, PM₁₀ and PM_2.5) were compared through a comprehensive statistical analysis including observational data from 165 monitoring stations all over the Iberian Peninsula. It was found that model sensitivity to BC for nitrogen and sulphur oxides was limited, being restricted to the vicinity of model boundaries. However, significant domain-wide differences were found when modelling ozone and PM depending on the BC provided to run the tests. Although model performance was affected by spatial and seasonal factors, the results indicate that model-derived, dynamic BC improved CMAQ predictions when compared to those based on static concentrations prescribed in the boundaries. Aggregated statistics suggest that the GEOS-Chem produced the best results for O₃ and PM_2.5 while NO₂ and PM₁₀ were slightly better predicted under the CMAQ nesting approach. Besides the statistical evaluation some other relevant issues in the context of Integrated Assessment Modelling (IAM) are discussed to gain a better insight into the suitability of the methods analyzed and limitations of downscaling methods. Despite being useful to get a better understanding of the role of BC in SIMCA, this study contributed to highlight model deficiencies and therefore to point out future research needs to improve IAM activities in the Iberian Peninsula.     

Characterisation of PM10 emissions from woodstove combustion of common woods grown in Portugal

A series of source tests was performed to evaluate the chemical composition of particle emissions from the woodstove combustion of four prevalent Portuguese species of woods: Pinus pinaster (maritime pine), Eucalyptus globulus (eucalyptus), Quercus suber (cork oak) and Acacia longifolia (golden wattle). Analyses included water-soluble ions, metals, radionuclides, organic and elemental carbon (OC and EC), humic-like substances (HULIS), cellulose and approximately l80 organic compounds. Particle (PM₁₀) emission factors from eucalyptus and oak were higher than those from pine and acacia. The carbonaceous matter represented 44–63% of the particulate mass emitted during the combustion process, regardless of species burned. The major organic components of smoke particles, for all the wood species studied, with the exception of the golden wattle (0.07–1.9% w/w), were anhydrosugars (0.2–17% w/w). Conflicting with what was expected, only small amounts of cellulose were found in wood smoke. As for HULIS, average particle mass concentrations ranged from 1.5% to 3.0%. The golden wattle wood smoke presented much higher concentrations of ions and metal species than the emissions from the other wood types. The results of the analysis of radionuclides revealed that the ²²⁶Ra was the naturally occurring radionuclide more enriched in PM₁₀. The chromatographically resolved organics included n-alkanes, n-alkenes, PAH, oxygenated PAH, n-alkanals, ketones, n-alkanols, terpenoids, triterpenoids, phenolic compounds, phytosterols, alcohols, n-alkanoic acids, n-di-acids, unsaturated acids and alkyl ester acids.     

Polycyclic aromatic hydrocarbons in air on small spatial and temporal scales – II. Mass size distributions and gas-particle partitioning

Polycyclic aromatic hydrocarbons (PAHs) were measured together with inorganic air pollutants at two urban sites and one rural background site in the Banja Luka area, Bosnia and Hercegovina, during 72 h in July 2008 using a high time resolution (5 samples per day) with the aim to study gas-particle partitioning, aerosol mass size distributions and to explore the potential of a higher time resolution (4 h-sampling).In the particulate phase the mass median diameters of the PAHs were found almost exclusively in the accumulation mode (0.1–1.0 μm of size). These were larger for semivolatile PAHs than for non-volatile PAHs. Gas-particle partitioning of semivolatile PAHs was strongly influenced by temperature. The results suggest that the Junge–Pankow model is inadequate to explain the inter-species variation and another process must be significant for phase partitioning which is less temperature sensitive than adsorption. Care should be taken when interpreting slopes m of plots of the type log K_p = m log p_L⁰ + b based on 24 h means, as these are found sensitive to the time averaging, i.e. tend to be higher than when based on 12 h-mean samples.