A national inventory to estimate release of polychlorinated dibenzo-p-dioxins and dibenzofurans in Portugal

Taking into account current environmental concerns, the main objective of this work focused a national inventory aiming to estimate the amount of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/PCDF) released in Portugal in 2006. The methodology used was based on the Standardized Toolkit for Identification and Quantification of Dioxins and Furan Releases, developed by UNEP Chemicals, in 2005. The method allows the assessment of the amount of PCDD/PCDF released into the environment along five vectors involving air, water, land, products and residues. Facing some difficulties mainly regarding to the availability of data for some activities known to produce PCDD/PCDF, three scenarios (Sc1 to Sc3) corresponding to lower, central and upper estimates were established. The Sc1 scenario (lower estimate) includes the situations where in case of doubt or scarce information, reduced or none emission values were assumed, Sc2 refers to a central estimate, which is believed to be the most realistic for the Portuguese situation, while Sc3 corresponds to the worst case (upper estimate). The results obtained pointed out that the total amount of PCDD/PCDF emitted in Portugal during the period under analysis was in the range of 51.2-217.9 g TEQ year⁻¹, with the most likely value of 95.2 g TEQ year⁻¹ achieved under the Sc2 scenario. This study also showed that the methodology developed by UNEP Chemicals is a very simple one, and the main difficulty is the availability of data. The main indicators calculated in this study were 8.98 μg TEQ/(year person) by taking into account the total amount of PCDD/PCDF released, and 3.63 μg TEQ/(year person) when only air emissions were considered.     

Acetylcholinesterase activity in the terrestrial snail Xeropicta derbentina transplanted in apple orchards with different pesticide management strategies

Apple orchards are highly manipulated crops in which large amounts of pesticides are used. Some of these pesticides lack target specificity and can cause adverse effects in non-target organisms. In order to evaluate the environmental risk of these products, the use of transplanted sentinel organisms avoids side-effects from past events and facilitate comparison of multiple sites in a short time. We released specimens of the terrestrial snail Xeropicta derbentina in each 5 of two kinds of apple orchards with either conventional or organic management strategies plus in a single abandoned orchard. After one month, individuals were retrieved in order to measure acetylcholinesterase (AChE) activity. Mean values of AChE activity were significantly reduced in all conventional apple orchards compared to the others. Results show that the measurement of biomarkers such as AChE inhibition in transplated X. derbentina could be useful in the environmental risk assessment of post-authorized pesticides.     

Effects of compositional heterogeneity and nanoporosity of raw and treated biomass-generated soot on adsorption and absorption of organic contaminants

A biomass-generated soot was sequentially treated by HCl-HF solution, organic solvent, and oxidative acid to remove ash, extractable native organic matter (EOM), and amorphous carbon. The compositional heterogeneity and nano-structure of the untreated and treated soot samples were characterized by elemental analysis, thermal gravimetric analysis, BET-N₂ surface area, and electron microscopic analysis. Sorption properties of polar and nonpolar organic pollutants onto the soot samples were compared, and individual contributions of adsorption and absorption were quantified. The sorption isotherms for raw sample were practically linear, while were nonlinear for the pretreated-soot. The removal of EOM enhanced adsorption and reduced absorption, indicating that EOM served as a partitioning phase and simultaneously masked the adsorptive sites. By drastic-oxidation, the outer amorphous carbon and the inner disordered core of the soot particles were completely removed, and a fullerene-like nanoporous structure (aromatic shell) was created, which promoted additional π-π interaction between phenanthrene and the soot.     

Variability of dust iron solubility in atmospheric waters: Investigation of the role of oxalate organic complexation

Atmospheric dust deposition is a major external iron source for remote surface ocean waters. Organic complexation is known to play a role in the dissolution of iron-containing minerals. In this paper, we present our study on the effect of oxalate on dust iron solubility in simulated rainwater. Our results reveal that the solubility of iron carried by analogs of different African dusts varies with the dust source. Our experiments indicate a positive linear correlation between iron solubility and oxalate concentration. Soluble iron (SFe) increases from 0.0025(±0.0005)% to 0.26(±0.01)% of total iron, considering all dust sources and with oxalate concentrations ranging from 0 to 8 μM. These results show that the observed variability of iron solubility in aerosols collected over the Atlantic Ocean is, at least partly, due to an increase in dust iron solubility, with the presence of oxalate complexation, rather than to the presence of more soluble anthropogenic iron. Considering the mineralogical composition of those particles, experiments with pure minerals (hematite, goethite and illite) were performed to study the dissolution process. We found that oxalate promotes the solubility of iron contained in clay and hence confirmed that more than 95% of SFe from soil dust is provided by clay (illite). This experimental work enables us to establish a parameterization of iron solubility in dust as a function of oxalate concentration and based on the individual iron solubility of pure iron-bearing minerals usually present in dust particles. Finally, our results emphasize that oxalate contributes to iron solubility on the same order of magnitude as the acid processes. Organic complexation appears to be a process that increases iron solubility and likely enhances the bioavailability of iron from dust.     

Recycling of organic materials and solder from waste printed circuit boards by vacuum pyrolysis-centrifugation coupling technology

Here, we focused on the recycling of waste printed circuit boards (WPCBs) using vacuum pyrolysis-centrifugation coupling technology (VPCT) aiming to obtain valuable feedstock and resolve environmental pollution. The two types of WPCBs were pyrolysed at 600°C for 30 min under vacuum condition. During the pyrolysis process, the solder of WPCBs was separated and recovered when the temperature range was 400-600°C, and the rotating drum was rotated at 1000 rpm for 10 min. The type-A of WPCBs pyrolysed to form an average of 67.91 wt.% residue, 27.84 wt.% oil, and 4.25 wt.% gas; and pyrolysis of the type-B of WPCBs led to an average mass balance of 72.22 wt.% residue, 21.57 wt.% oil, and 6.21 wt.% gas. The GC-MS and FT-IR analyses showed that the two pyrolysis oils consisted mainly of phenols and substituted phenols. The pyrolysis oil can be used for fuel or chemical feedstock for further processing. The recovered solder can be recycled directly and it can also be a good resource of lead and tin for refining. The pyrolysis residues contained various metals, glass fibers and other inorganic materials, which could be recovered after further treatment. The pyrolysis gases consisted mainly of CO, CO(2), CH(4), and H(2), which could be collected and recycled.     

Trace elements and microbiological parameters in farmed Nile tilapia with emphasis on muscle,water, sediment and feed

Fish may bioaccumulate contaminants from the aquatic environment and extend them to the food chain provoking risks to human health. This study evaluated the microbiological parameters of the pond´s water and trace elements concentrations in samples of water, sediment, feed and muscle of farmed Nile tilapia used for human consumption in southern Brazil. A total of 240 fish were collected from 12 tilapia farms. Sediment, tank water and dry ration used in the animals' diet were collected for analysis. Analysis were performed by Energy Dispersion X-ray Fluorescence (EDXRF), Inductively Coupled Plasma Mass Spectrometer (ICP-MS), Induced Coupled Plasma Optical Emission Spectrometer (ICP-OES), and Atomic Absorption Spectrometer (AAS-VGA). In addition, the microbiological analysis of the water was carried out. The concentrations of Se, I, Fe, Cu and Zn in fish muscle were higher than the recommended by the Brazilian legislation, considering the advised daily intake for adults. The arsenic element had concentrations above the limit stipulated by the present Brazilian legislation, observed in all samples of muscle, sediment and tank water highlighting a possible environmental and fish contamination by the toxic element. Moreover, the arsenic concentration in the water presented a positive correlation (ρ?=?0.33) with arsenic in the muscle, suggesting that tilapia is a good environmental bioindicator, once they properly reflect the levels of arsenic in the water. It is suggested to perform an arsenic speciation for quantification of the inorganic form and accurate assessment of the degree of toxicity in the muscle samples and risks it can bring to human health. Regarding the other potentially toxic elements (Hg, Pb and Cd), and microbiological analysis of water it was verified that the consumption of the fish in question does not raise risks, since the values are within a quality benchmark established by law. The concentration of total and fecal coliforms in pond´s water in the facilities was in agreement with the microbiological indexes required by the legislation of CONAMA class II. Western region presented the lowest concentrations of fecal coliforms when compared to the other regions. There was no significant difference in the microbiological counts of total heterotrophic bacteria, Vibrio spp. and Pseudomonas spp. among the regions.     

A new direct thermal desorption-GC/MS method: Organic speciation of ambient particulate matter collected in Golden, BC

Particulate matter having an aerodynamic diameter less than 2.5 μm (PM2.5) is thought to be implicated in a number of medical conditions, including cancer, rheumatoid arthritis, heart attack, and aging. However, very little chemical speciation data is available for the organic fraction of ambient aerosols. A new direct thermal desorption-gas chromatography/mass spectrometry (TD-GC/MS) method was developed for the analysis of the organic fraction of PM2.5. Samples were collected in Golden, British Columbia, over a 15-month period. n-Alkanes constituted 33–98% by mass of the organic compounds identified. PAHs accounted for 1–65% and biomarkers (hopanes and steranes) 1–8% of the organic mass. Annual mean concentrations were: n-alkanes (0.07–1.55 ng m⁻³), 16 PAHs (0.02–1.83 ng m⁻³), and biomarkers (0.02–0.18 ng m⁻³). Daily levels of these organics were 4.89–74.38 ng m⁻³, 0.27–100.24 ng m⁻³, 0.14–4.39 ng m⁻³, respectively. Ratios of organic carbon to elemental carbon (OC/EC) and trends over time were similar to those observed for PM2.5. There was no clear seasonal variation in the distribution of petroleum biomarkers, but elevated levels of other organic species were observed during the winter. Strong correlations between PAHs and EC, and between petroleum biomarkers and EC, suggest a common emission source – most likely motor vehicles and space heating.     

Volatilization characteristics of organic solutes in stirred solution

The effects of turbulence intensity (velocity gradient, G (s⁻¹)), Henry's law constant (H), and molecular weight (M) on the volatilization rates of organic compounds are examined using changes in the mass transfer coefficients (K_OL (cm/min)) under specific liquid-mixing intensities. The selected compounds were divided into three groups according to their H values (mole in gas/mole in liquid, dimensionless), which ranged from 10² to 10⁻⁵. The relationship of the K_OL relative to G, H and M was obtained via multiple regression. The obtained values of these parameters indicate that the primary factor affecting the K_OL values of the high H compounds is their M values. The effects of the H values on the K_OL values of the high H compounds can be neglected. On the other hand, the H value is the major factor determining the K_OL values of the low H compounds. The changes in the K_OL values of the different H compounds exhibit different profiles as the liquid-mixing intensity increases. The M and H values of middle H compounds possibly affect their K_OL values. The effects of the liquid-mixing intensity on the K_OL values of the organic compounds increase with increasing H values. The variation in the K_OL values might be a result of the concentration of the organic compounds at the interface between the liquid and gas films. The empirical relationship between K_OL and some selected parameters, G, H and M, is examined in this study. The obtained results can help to estimate volatilization loss of organic solutes in wastewater treatment facilities.     

One laptop per child,local refurbishment or overseas donations? Sustainability assessment of computer supply scenarios for schools in Colombia

With the intention of bridging the ‘digital divide’ many programmes have been launched to provide computers for educational institutions, ranging from refurbishing second hand computers to delivering low cost new computers. The fast and economical provision of large quantities of equipment is one of the many challenges faced by such programmes. If an increase is to be achieved in the sustainability of computer supplies for schools, not only must equipment be provided, but also suitable training and maintenance delivered. Furthermore, appropriate recycling has to be ensured, so that end-of-life equipment can be dealt with properly. This study has evaluated the suitability of three computer supply scenarios to schools in Colombia: (i) ‘Colombian refurbishment’, -refurbishment of computers donated in Colombia, (ii) ‘Overseas refurbishment’, -import of computers which were donated and refurbished abroad, and (iii) ‘XO Laptop’, -purchase of low cost computers manufactured in Korea. The methods applied were: Material Flow Assessment, -to assess the quantities-, Life Cycle Assessment, -to assess the environmental impacts, and the application of the Multiple Attribute Utility Theory, -to analyse, evaluate and compare different scenarios. The most sustainable solution proved to be the local refurbishment of second hand computers of Colombian origin to an appropriate technical standard. The environmental impacts of such practices need to be evaluated carefully, as second hand appliances have to be maintained, require spare parts and sometimes use more energy than newer equipment. Providing schools with second hand computers from overseas and through programmes such as ‘One Laptop Per Child’ has the disadvantage that the potential for social improvements – such as creation of jobs and local industry involvement – is very low.     

Effects of dredging on benthic diatom assemblages in a lowland stream

The objective of this study was to assess the effects of dredging on the structure and composition of diatom assemblages from a lowland stream and to investigate whether the response of diatom assemblages to the dredging is also influenced by different water quality. Three sampling sites were established in Rodríguez Stream (Argentina); physico-chemical variables and benthic diatom assemblages were sampled weekly in spring 2001. Species composition, cell density, diversity and evenness were estimated. Diatom tolerance to organic pollution and eutrophication were also analyzed. Differences in physico-chemical variables and changes in benthic diatom assemblages were compared between the pre- and post-dredging periods using a t-test. Data were analyzed using Principal Components Analysis (PCA), non-metric multidimensional scaling (MDS) ordination and cluster analysis. The effects of dredging in the stream involve two types of disturbances: (i) in the stream bed, by the removal and destabilization of the substrate and (ii) in the water column, by generating chemical changes and an alteration of the light environment of the stream. Suspended solids, soluble reactive phosphorus and dissolved inorganic nitrogen were significantly higher in post-dredging periods. Physical and chemical modifications in the habitat of benthic diatoms produced changes in the assemblage; diversity and species numbers showed an immediate increase after dredging, decreasing at the end of the study period. Changes in the tolerance of the diatom assemblage to organic pollution and eutrophication were also observed as a consequence of dredging; in the post-dredging period sensitive species were replaced by either tolerant or most tolerant species. These changes were particularly noticeable in site 1 (characterized by its lower amount of nutrients and organic matter previous to dredging), which showed an increase in the amount of nutrients and oxygen demand as a consequence of sediment removal. However, these changes were not so conspicuous in sites 2 and 3, which already presented a marked water quality deterioration before the execution of the dredging works.