The effects of accelerated carbonation on CO2 uptake and metal release from incineration APC residues

This work presents the results of a study on accelerated carbonation of incinerator air pollution control residues, with a particular focus on the modifications in the leaching behaviour of the ash. Aqueous carbonation experiments were carried out using 100% CO₂ at different temperatures, pressures and liquid-to-solid ratios, in order to assess their influence on process kinetics, CO₂ uptake and the leaching behaviour of major and trace elements. The ash showed a particularly high reactivity towards CO₂, owing to the abundance of calcium hydroxides phases, with a maximum CO₂ uptake of ～250 g/kg. The main effects of carbonation on trace metal leaching involved a significant decrease in mobility for Pb, Zn and Cu at high pH values, a slight change or mobilization for Cr and Sb, and no major effects on the release of As and soluble salts. Geochemical modelling of leachates indicated solubility control by different minerals after carbonation. In particular, in the stability pH range of carbonates, solubility control by a number of metal carbonates was clearly suggested by modelling results. These findings indicate that accelerated carbonation of incinerator ashes has the potential to convert trace contaminants into sparingly soluble carbonate forms, with an overall positive effect on their leaching behaviour.     

Performance of a biogas upgrading process based on alkali absorption with regeneration using air pollution control residues

This work analyzes the performance of an innovative biogas upgrading method, Alkali absorption with Regeneration (AwR) that employs industrial residues and allows to permanently store the separated CO₂. This process consists in a first stage in which CO₂ is removed from the biogas by means of chemical absorption with KOH or NaOH solutions followed by a second stage in which the spent absorption solution is contacted with waste incineration Air Pollution Control (APC) residues. The latter reaction leads to the regeneration of the alkali reagent in the solution and to the precipitation of calcium carbonate and hence allows to reuse the regenerated solution in the absorption process and to permanently store the separated CO₂ in solid form. In addition, the final solid product is characterized by an improved environmental behavior compared to the untreated residues. In this paper the results obtained by AwR tests carried out in purposely designed demonstrative units installed in a landfill site are presented and discussed with the aim of verifying the feasibility of this process at pilot-scale and of identifying the conditions that allow to achieve all of the goals targeted by the proposed treatment. Specifically, the CO₂ removal efficiency achieved in the absorption stage, the yield of alkali regeneration and CO₂ uptake resulting for the regeneration stage, as well as the leaching behavior of the solid product are analyzed as a function of the type and concentration of the alkali reagent employed for the absorption reaction.     

Analysing the fate of nanopesticides in soil and the applicability of regulatory protocols using a polymer-based nanoformulation of atrazine

For the first time, regulatory protocols defined in the OECD guidelines were applied to determine the fate properties of a nanopesticide in two agricultural soils with contrasting characteristics. The nanoformulation studied had no effect on the degradation kinetics of atrazine indicating that (1) the release of atrazine from the polymer nanocarriers occurred rapidly relative to the degradation kinetics (half-lives 36–53 days) and/or that (2) atrazine associated with the nanocarriers was subject to biotic or abiotic degradation. Sorption coefficients, derived from a batch and a centrifugation technique at a realistic soil-to-solution ratio, were higher for the nanoformulated atrazine than for the pure active ingredient. Results indicate that the nanoformulation had an effect on the fate of atrazine. However, since the protocols applied were designed to assess solutes, conclusions about the transport of atrazine loaded onto the nanocarriers should be made extremely cautiously. The centrifugation method applied over time (here over 7 days) appears to be a useful tool to indirectly assess the durability of nanopesticides under realistic soil-to-solution ratios and estimate the period of time during which an influence on the fate of the active ingredient may be expected. More detailed investigations into the bioavailability and durability of nanopesticides are necessary and will require the development of novel methods suitable to address both the “nano” and “organic” characteristics of polymer-based nanopesticides.     

Chemical Characterization of Soil Used as a Deposit for Waste Originating From the Manufacturing of Products Based on Fiberglass

Companies need to follow environmental laws as they affect their manufacturing systems, waste handling, and the management of soil on their properties to ensure that their properties are either improved or altered as little as possible. Thus, the objective of this study was to evaluate the use of energy dispersive X‐ray fluorescence spectrometry (EDXRF) to determine the concentrations of elements present in the soil at a manufacturer of products based on fiberglass where wastes from production activities have been deposited on the property.     

Health risks of environmental exposure to metals and herbicides in the Pardo River,Brazil

Mixture of metals and herbicides in rivers may pose relevant risks for the health of surrounding communities. Humans may be exposed to river pollution through intake of contaminated water and fish, as well as irrigated agricultural products. The aim of this study was to assess the human health risks of environmental exposure to metals and herbicides through water and fish intake in the Pardo River. Metals (Al, As, Be, Cd, Cr, Cu, Pb, Mn, Hg, Ni, Tl, Sn, V, and Zn) were analyzed in river water and in edible fish. Herbicides (ametryn, atrazine, diuron, hexazinone, simazine, and tebuthiuron) were analyzed in river water. Seasonal variances were also studied. Aluminum, Cd, Cu, Mn, Pb, and Zn levels in river water were higher than the USEPA benchmarks. Non-carcinogenic risks due to pollutants mixture exposure were above the limit, and carcinogenic risks of As exposure were >10^?6 in the sampling points during the rainy season. Metal levels in fish were lower than the Brazilian legislation and do not pose a threat to public health. Herbicides were detected in four sampling points, with atrazine concentrations (range 0.16–0.32 μg/L) below the Brazilian standard (2.0 μg/L), but above the European Union standard (0.1 μg/L). Considering the water supply needs of cities located in the Pardo River Basin and the persistence of metals and herbicides, the present study indicated that there was a seasonal influence on non-carcinogenic and carcinogenic risks to human health, especially in the rainy season. Studies for water treatment plants implantation should consider the risks of exposure to persistent substances, in order to protect the population.     

Transboundary Socio-Ecological Effects of a Marine Protected Area in the Southwest Atlantic

Marine Protected Areas (MPAs) have been regarded as an alternative to protect natural resources and to improve fisheries. However, MPAs may also have negative socio-economic consequences on fishing communities. We aimed to check the effectiveness of a socially conflicting MPA in Brazil by assessing target reef fish biomass in islands inside (n = 6) and outside (n = 6) the MPA, fisheries’ productivity (biomass), catch per unit of effort (CPUE), and fishers’ socio-economic status (mainly fishers’ income) in three fishing communities subjected to different degrees of influence (close, average, and long distance) of the MPA. The CPUE was higher in the fishing community that was further away from the MPA, fish biomass was higher in the islands located inside the MPA in the southern region and in the islands located outside the MPA in the northern region, while fishers were making the most money closest to the MPA, where conflicts are the highest, probably from practicing very intensive fisheries. This integrated approach showed that the studied MPA has not delivered ecological benefits, such as higher CPUE or more fish, while higher income closer to the MPA could not be clearly attributed to its effects.     

Modeling of vapor intrusion from hydrocarbon-contaminated sources accounting for aerobic and anaerobic biodegradation

A one-dimensional steady state vapor intrusion model including both anaerobic and oxygen-limited aerobic biodegradation was developed. The aerobic and anaerobic layer thickness are calculated by stoichiometrically coupling the reactive transport of vapors with oxygen transport and consumption. The model accounts for the different oxygen demand in the subsurface required to sustain the aerobic biodegradation of the compound(s) of concern and for the baseline soil oxygen respiration. In the case of anaerobic reaction under methanogenic conditions, the model accounts for the generation of methane which leads to a further oxygen demand, due to methane oxidation, in the aerobic zone. The model was solved analytically and applied, using representative parameter ranges and values, to identify under which site conditions the attenuation of hydrocarbons migrating into indoor environments is likely to be significant. Simulations were performed assuming a soil contaminated by toluene only, by a BTEX mixture, by Fresh Gasoline and by Weathered Gasoline. The obtained results have shown that for several site conditions oxygen concentration below the building is sufficient to sustain aerobic biodegradation. For these scenarios the aerobic biodegradation is the primary mechanism of attenuation, i.e. anaerobic contribution is negligible and a model accounting just for aerobic biodegradation can be used. On the contrary, in all cases where oxygen is not sufficient to sustain aerobic biodegradation alone (e.g. highly contaminated sources), anaerobic biodegradation can significantly contribute to the overall attenuation depending on the site specific conditions.     

Use of the digestive gland of the oyster Crassostrea rhizophorae (Guilding, 1828) as a bioindicator of Zn,Cd and Cu contamination in estuarine sediments (south-east Brazil)

This study demonstrates the accumulation of Zn, Cd and Cu in the digestive gland of the oyster Crassostrea rhizophorae in response to the contamination of sediments and discusses the potential use of this specific organ in monitoring metal contamination in tropical areas. Sediment and oyster samples were collected from coastal Rio de Janeiro sites with different levels of human impact: Sepetiba Bay, Guanabara Bay and the Paraty coast. Metal concentrations were measured using inductively coupled plasma optical emission spectrometry (ICP OES). Significant statistical differences (p<0.001; p<0.05) were observed for Zn and Cd concentrations in the digestive gland; the highest Zn concentrations were found at Sepetiba, followed by Guanabara and Paraty. The highest digestive gland Cd concentrations were found at Paraty, followed by Sepetiba and Guanabara. These concentrations were proportional to those found in the sediments. There was no significant difference (p>0.05) in Cu among the sampling sites. The highest digestive-gland Cu concentration was also found at Sepetiba, followed by Guanabara. The biosediment accumulation factor indicated a gradient of sediment contamination for Zn and Cd. The digestive gland of C. rhizophorae can be a potential indicator of trace metal contamination in sediments from tropical estuarine environments.     

Stressed, but not defenceless: no obvious influence of irradiation levels on antifeeding and antifouling defences of tropical macroalgae

The production of defence metabolites is assumed to be costly in metabolic terms. If this holds true, low-light stress should reduce the ability of seaweeds to defend themselves chemically against herbivory and fouling. We investigated the effect of energy limitation on the defensive status of seaweeds by assessing their attractiveness to mesograzers and their activity against a bivalve macrofouler in comparison with non-stressed conspecifics. The macroalgae Codium decorticatum (Woodw.) M. Howe, Osmundaria obtusiloba (C. Agardh) R. E. Norris, Pterocladiella capillacea (S. G. Gmel.) Santel. and Hommer., Sargassum vulgare C. Agardh and Stypopodium zonale (Lamour.) Papenf. collected at the southeastern Brazilian coast were exposed to six levels of irradiation (between 1 and 180 μmol photons m⁻² s⁻¹) for 10–14 days. After this period, algae from all treatment levels were: (a) processed as artificial food and offered to an amphipod community dominated by Elasmopus brasiliensis Dana and (b) extracted to test for differences in settlement rates of the fouling mussel Perna perna L. on filter paper loaded with the crude extracts. Generally, photosynthesis rates and growth were reduced under low light conditions. Attractiveness to herbivores and macrofoulers, however, was insensitive to energy limitation. We discuss possible explanations for the observed absence of a relationship between light availability and algal defence including the change in nutritional value of the algal tissue, the allocation of resources towards defence instead of growth and the absence of costs for defence.     

Integral transform solutions for atmospheric pollutant dispersion

A transient two-dimensional advection–diffusion model describing the turbulent dispersion of pollutants in the atmosphere has been solved via the Generalized Integral Transform Technique (GITT), by two different schemes. The first approach performs numerical integration of the transformed system using available routines for initial value problems with automatic error control. In spite of the time-consuming character of such a scheme, its flexibility allows the handling of problems involving time-dependent meteorological parameters such as wind speed and eddy diffusivities. The second approach works fully analytically being thus intrinsically more robust and economic, although not directly applicable in dealing with time-dependent parameters. For the test problem used in this work, both methods agree very well with each other, as well as with a known analytical solution for a simpler formulation used as benchmark. The impact of the longitudinal diffusivity on the stiffness of the ordinary differential equation (ODE) system arising from the integral transformation has been assessed through the processing time demanded to solve it when the numerical approach is used. The observed CPU times show that the analytical approach is clearly preferable unless the problem involves time-dependent parameters.