Determination of direct and fugitive PM emissions in a Mediterranean harbour by means of classic and novel tracer methods

Remodelling works are frequent in harbour areas, given that they must adapt to rapidly changing market requirements. Depending on their nature (construction, demolition, etc.), these works may be carried out during long periods of time and thus exert a significant impact on the air quality at the harbours and their surroundings. The air quality at the Valencia harbour was studied during an enlargement project. Four sampling stations aimed to cover the major dust-emitting activities in the harbour. In addition, a sampling campaign was carried out to collect dust materials at their emission sources (e.g., loading and unloading of clinker and petroleum coke, as well as the enlargement works). Differences obtained between PM levels at the monitoring sites were correlated with the distance between sampling stations and enlargement works and/or harbour operations, as well as with the preferential wind direction. In all cases, the days with the highest PM_10 levels were linked to wind directions coinciding with the location of the enlargement works or the clinker and petroleum coke stocks. Classic source apportionment methodologies (PCA and CMB) were applied to the data, but their interpretation was complex due to the similar chemical signatures of PM originating from direct and fugitive emissions from stocked materials (e.g., clinker), and the enlargement works. To overcome this difficulty, a novel non-statistical approach was used to obtain quantitative estimations of the contributions from sources (petroleum coke and clinker), based on the correlation between specific PM components (e.g., carbonaceous species) and source tracers (e.g., V). Finally, a qualitative test using phenolphthalein was devised to identify the presence of clinker on the filters, which provided positive results. This novel tracer approach is thus recommended for harbour authorities.     

Sorption and leaching potential of acidic herbicides in Brazilian soils

Leaching of acidic herbicides (2,4-D, flumetsulam, and sulfentrazone) in soils was estimated by comparing the original and modified AF (Attenuation Factor) models for multi-layered soils (AFi). The original AFi model was modified to include the concept of pH-dependence for Kd (sorption coefficient) based on pesticide dissociation and changes in the accessibility of soil organic functional groups able to interact with the pesticide. The original and modified models, considering soil and herbicide properties, were applied to assess the leaching potential of selected herbicides in three Brazilian soils. The pH-dependent Kd values estimated for all three herbicides were observed to be always higher than pH-independent Kd values calculated using average Koc data, and therefore the original AFi model overestimated the overall leaching potential for the soils studied.     

Effects of body mass,age, dominance and parasite load on foraging time of bighorn rams,<Emphasis Type="Italic"> Ovis canadensis</Emphasis>

In sexually dimorphic ungulates, males generally spend less time foraging than females, possibly because of difference in body mass or because of the energetic requirements of lactation. The relationship between body size and foraging time has received little attention at the intra-specific level, because few studies have documented activity budgets for individuals of known size. Bighorn rams are a good model to explore how body mass affects foraging time, because they range in mass from 55 to 140 kg. We examined how the foraging time of bighorn rams varied according to individual characteristics. We observed rams in a marked population and constructed time budgets during the 3 months preceding the rut. We determined ram social rank based on agonistic encounters and collected fecal samples to count lungworm larvae. Time spent foraging was negatively correlated with body mass. After accounting for age differences, larger rams spent less time foraging and more time lying than smaller rams. Among rams aged 6–12 years, dominants spent less time feeding than subordinates, while fecal output of lungworm larvae was negatively correlated with foraging time for rams of all ages. Body mass accounts for much of the individual variation in foraging time, suggesting that sexual dimorphism is important in explaining differences in feeding time between males and females.Communicated by P. Heeb     

Effects of spatial autocorrelation and sampling design on estimates of protected area effectiveness

Estimating the effectiveness of protected areas (PAs) in reducing deforestation is useful to support decisions on whether to invest in better management of areas already protected or to create new ones. Statistical matching is commonly used to assess this effectiveness, but spatial autocorrelation and regional differences in protection effectiveness are frequently overlooked. Using Colombia as a case study, we employed statistical matching to account for confounding factors in park location and accounted for for spatial autocorrelation to determine statistical significance. We compared the performance of different matching procedures—ways of generating matching pairs at different scales—in estimating PA effectiveness. Differences in matching procedures affected covariate similarity between matched pairs (balance) and estimates of PA effectiveness in reducing deforestation. Independent matching yielded the greatest balance. On average 95% of variables in each region were balanced with independent matching, whereas 33% of variables were balanced when using the method that performed worst. The best estimates suggested that average deforestation inside protected areas in Colombia was 40% lower than in matched sites. Protection significantly reduced deforestation, but PA effectiveness differed among regions. Protected areas in Caribe were the most effective, whereas those in Orinoco and Pacific were least effective. Our results demonstrate that accounting for spatial autocorrelation and using independent matching for each subset of data is needed to infer the effectiveness of protection in reducing deforestation. Not accounting for spatial autocorrelation can distort the assessment of protection effectiveness, increasing type I and II errors and inflating effect size. Our method allowed improved estimates of protection effectiveness across scales and under different conditions and can be applied to other regions to effectively assess PA performance.     

Metal distribution in marine sediments of the Mar Piccolo in Taranto (Ionic Sea,southern Italy)

The spatial distribution of selected metals (Fe, Ni, Mn, Zn, Cu, Pb, Hg and Cd) and their partition in the different chemical forms (speciation) were determined in benthic sediments from Mar Piccolo, Taranto (Ionic Sea, southern Italy). The aim of this study was to assess the degree of sediment contamination and bioavailability of metals, very important for Italian mussel culture, in a semi-enclosed marine ecosystem. In sediments, grain size distribution, total organic carbon (TOC), and humic (HA) and fulvic (FA) acids contents were also determined. The compounds TOC, HA and FA, in fact, have a great influence on metal complexation. High concentrations of copper, lead, zinc and mercury were found, especially in sediments of the first inlet of Mar Piccolo. Statistical analysis of results shows significant correlation among Cu, Pb and Zn concentrations and the influence of organic matter on the sediment distribution of Cu, Pb and Zn. Metal speciation analysis, carried out with sequential extraction method, shows that Fe and Ni are present in sediments mainly as sulphides. Mn and Pb are present principally in an ion-exchangeable form or bound to carbonate and Cu is associated to organic matter. Metal pollution index (MPI), calculated as a weighed mean of the metal contamination factors in each station, shows that with regard to Cu, Ni, Pb and Zn, some stations investigated are unpolluted (MPI <1), whereas in other areas, pollution level is not very high. On the contrary, for mercury, the pollution level in the first inlet of the basin is very high.     

Rhythmic vertical migration of the gastropod Cerithidea decollata in a Kenyan mangrove forest

In Mida Creek, Kenya (3°20′S, 40°5′E), at high water, the snail Cerithidea decollata dwells on the trunks of mangrove trees (Avicennia marina), while during low water it migrates to the ground, foraging at various distances from the trunk, where it aggregates again well before the incoming tide. Snails from the upper shore level are 150–200 m distant from those living at the lower shore level and they cluster at lower heights on trunks. In any case, sufficient height is usually attained to avoid being submersed. An experiment was designed (February and October 2005), exchanging individuals from different shore levels subject to different tide regimes, in order to test whether snails rely on internal information or on external, direct cues, to adapt their behaviour to local conditions. Results show that C. decollata mostly rely on internal information, presumably based on an internal clock. When individuals from upper and lower shore levels were exchanged, their internal clocks continued to govern when to ascend the home trunk and how high to climb for five to six successive tides, after which the behaviour was reset to the new local conditions.     

UVR-induced photoinhibition of summer marine phytoplankton communities from Patagonia

During austral summer 2006, experiments were carried out to evaluate the effects of ultraviolet radiation (UVR, 280–400 nm) on carbon fixation of natural phytoplankton assemblages from Patagonia (Argentina). Surface water samples were collected (ca. 100 m offshore) at mid morning using an acid-cleaned (1 N HCl) dark container. The short-term impact of UVR (measured as radiocarbon incorporation) was immediately assessed by exposing samples to three artificial illumination treatments: PAR (400–700 nm), PAR + UV-A (320–700 nm), and PAR + UV-A + UV-B (280–700 nm). Pico-nanoplankton characterized the assemblages, and taxon-specific pigment fingerprinting combined with CHEMTAX and supplemented with microscopic observations showed varied proportions of diatoms, chlorophytes, and cyanobacteria throughout January–February 2006. Photosynthetic efficiency, as assessed through assimilation numbers, was high [between 4.4 and 10.4 μg C (μg chl-a)⁻¹ h⁻¹], and it was probably favored by the supply of inorganic nutrients from the Chubut River. UVR-induced photoinhibition appeared to be related to the taxonomic composition: in general, higher photoinhibition was observed when diatoms dominated, whereas this was lower when samples were dominated by chlorophytes. Our data suggest that xanthophyll pigments might have provided only limited protection in these already highlighted acclimated assemblages.     

Geophysical and hydrological data assimilation to monitor water content dynamics in the rocky unsaturated zone

In recent years, geophysics is increasingly used to study the flow and transport processes in the vadose zone. Particularly, when the vadose zone is made up of rocks, it is difficult to install sensors in the subsurface to measure hydrological state variables directly. In these cases, the electrical resistivity tomography (ERT) represents a useful tool to monitor the hydrodynamics of the infiltration and to estimate hydraulic parameters and state variables, such as hydraulic conductivity and water content. We propose an integrated approach aimed at predicting water content dynamics in calcarenite, a sedimentary carbonatic porous rock. The uncoupled hydrogeophysical approach proposed consists in 4D ERT monitoring conducted during an infiltrometer test under falling head conditions. Capacitance probes were installed to measure water content at different depths to validate the estimations derived from ERT. A numerical procedure, based on a data assimilation technique, was accomplished by combining the model (i.e., Richards’ equation) with the observations in order to provide reliable water content estimations. We have used a new data assimilation method that is easy to implement, based on the ensemble Kalman filter coupled with Brownian bridges. This approach is particularly suitable for strongly non-linear models, such as Richards’ equation, in order to take into account both the model uncertainty and the observation errors. The proposed data assimilation approach was tested for the first time on field data. A reasonable agreement was found between observations and predictions confirming the ability of the integrated approach to predict water content dynamics in the rocky subsoil.     

Deactivation and regeneration of ZSM-5 zeolite in catalytic pyrolysis of plastic wastes

In this work, a study of the regeneration and reuse of ZSM-5 zeolite in the pyrolysis of a plastic mixture has been carried out in a semi-batch reactor at 440 °C. The results have been compared with those obtained with fresh-catalyst and in non-catalytic experiments with the same conditions. The use of fresh catalyst produces a significant change in both the pyrolysis yields and the properties of the liquids and gases obtained. Gases more rich in C3-C4 and H₂ are produced, as well as lower quantities of aromatic liquids if compared with those obtained in thermal decomposition. The authors have proved that after one pyrolysis experiment the zeolite loses quite a lot of its activity, which is reflected in both the yields and the products quality; however, this deactivation was found to be reversible since after regeneration heating at 550 °C in oxygen atmosphere, this catalyst recovered its initial activity, generating similar products and in equivalent proportions as those obtained with fresh catalyst.     

Mass balanced and dynamic simulations of trophic models of kelp ecosystems near the Mejillones Peninsula of northern Chile (SE Pacific): Comparative network structure and assessment of harvest strategies

Mass balanced trophic models for kelp ecosystems which include subsystems dominated by Macrocystis integrifolia, Lessonia trabeculata and areas of barren ground (BG) were constructed for subtidal areas near the Mejillones Peninsula (SE Pacific), Chile. Information on biomass, P/B ratios, catches, food spectrum, consumption and dynamics of commercial and non-commercial populations was obtained and examined using Ecopath with Ecosim software analyses. The biomass of blades of L. trabeculata and M. integrifolia represented the compartments most relevant to the subsystems studied. Within the herbivores, the sea urchin Tetrapigus niger was dominant, followed by the snails Turritella sp. and Tegula sp. The fishes Pinguipes chilensis and Cheilodactylus variegatus were the dominant predators, followed by the asteroids Heliaster helianthus and Meyenaster gelatinosus. The highest system throughput (72,512 g wet weight m⁻² year⁻¹) was calculated for the subsystem dominated by M. integrifolia. The mean trophic level of the catch ranged from 1.1 (subsystem dominated by L. trabeculata) to 1.3 (subsystem dominated by M. integrifolia) to 3.2 (barren ground subsystem), showing that harvesting in each system was concentrated either on primary producers (blades of kelp species) or top predator fishes. Although the values for the Relative Ascendency (A/C) fluctuated from 36.5 to 45%, suggesting that all the systems were immature, the subsystem dominated by M. integrifolia emerged as the least resistant to external disturbances (e.g. fisheries). This result agreed with the high value of the system recovery time (SRT) for the M. integrifolia subsystem as a response to combined fisheries scenarios. The results obtained using mixed trophic impact (MTI) and Ecosim [increasing the fishing mortality F_i by 4×] showed that in most of the cases the predictions had the same qualitative tendencies. One of the most important results obtained in this study was that exploitation of kelp blades as an alternative strategy to harvesting the whole plants appeared to be ecologically sustainable, since harvesting the blades propagated only small effects on the entire subsystem. The fish P. chilensis may be considered as a top predator species with a strong top-down control since an increase in its fishing mortality in the subsystem dominated by M. integrifolia produced a high SRT value, and the F_MSY was less than the originally entered F_i in Ecopath. Based on the results obtained, it was concluded that the trophic mass balanced models and simulated management scenarios offered good possibilities for the planning of interventions and manipulations or the planning of more sustainable management strategies in highly disturbed natural systems.