Modelagem analítica e experimental da filtração em meios porosos

Deep bed filtration occurs in several industrial and environmental processes like water filtration and soil contamination. In petroleum industry, deep bed filtration occurs near to injection wells during water injection, causing injectivity reduction. It also takes place during well drilling, sand production control, produced water disposal in aquifers, etc. The particle capture in porous media can be caused by different physical mechanisms (size exclusion, electrical forces, bridging, gravity, etc). A statistical model for filtration in porous media is proposed and analytical solutions for suspended and retained particles are derived. The model, which incorporates particle retention probability, is compared with the classical deep bed filtration model allowing a physical interpretation of the filtration coefficients. Comparison of the obtained analytical solutions for the proposed model with the classical model solutions allows concluding that the larger the particle capture probability, the larger the discrepancy between the proposed and the classical models

Avaliação da correlação entre os parâmetros, carbono orgânico total e elementos tóxicos, em solo de um posto de serviço e revenda de combustíveis

Today a major responsibility for the contamination of soil and groundwater and surface water are establishments known as gas stations of fuel which has attracted increasing attention from both the general population as the state agencies of environmental control due to leaks in storage tanks and mainly to disruption of pipe corrosion of tanks and pumping. Other services, like oil changes and car wash are also causes for concern in this type of establishment. These leaks can cause or waste produced, and the contamination of aquifers, serious health problems and public safety, since most of these stations located in urban areas. Based on this, the work was to evaluate soil contamination of a particular service station and fuel sales in the city of Natal, through the quantification of heavy metals like Cd, Cu, Cr, Ni, Pb, Zn of total organic carbon (TOC) and organic matter using different techniques such as optical emission spectrometry with inductively coupled plasma source (ICP OES), Total Organic Carbon analyzer and gravimetric analysis respectively. And also to characterize the soil through particle size analysis. Samples were taken in 21 georeferenced points and collected in the same period. The soils sampled in sampling stations P3, P5, P6, P10, P11, P12, P13, P14, P15, P17, P18 and P20 showed the smallest size fractions ranging from fine sand to medium sand. The other study sites ranged from fine sand to medium sand, except the point P8 showed that only the type size medium sand and P19, indicating a particle size of the coarse type. The small correlation of organic matter with the elements studied in this work suggests that these are not of anthropogenic origin but geochemical support

Fitoextracção de cádmio de solos contaminados, com plantas seleccionadas

A remediação de locais contaminados com metais pesados usando plantas hiperacumuladoras aparenta ser uma alternativa bastante viável. Neste trabalho comparou-se a acumulação e tolerância ao cádmio (Cd), ambas baseadas nas respostas ao stress oxidativo em três espécies de plantas diferentes: Brassica juncea (L.) Czem., Nicotiana tabacum L. e Solanum nigrum L., descritas na literatura como plantas bastante tolerantes ou até com características híper acumuladoras. As plantas cresceram num solo contaminado com diferentes concentrações de Cd (O- 35 mg kg-1) durante um período de 90 dias. O factor de translocação (FT), utilizado para medir a translocação efectiva do Cd da raiz para a parte aérea, variou consideravelmente entre as espécies desenvolvidas. A N. tabacum foi a planta que apresentou os maiores valores de FT. Neste trabalho foi a única planta que preencheu todas as condições para ser considerada hiperacumuladora para todos os níveis de contaminação do solo. Por outro lado, a S. nigrum apresentou os maiores valores de concentração de Cd nos tecidos, com um FT > 1, na presença de 5 mg Cd kg·1 de solo. Apesar da B. juncea ter apresentado um resultado de FT inferior às restantes, foi a única planta com valores crescentes de FT com o aumento da contaminação de Cd. O stress oxidativo nas plantas desenvolvidas foi avaliado pela peroxidação lipídica e pelas actividades da catalase (CAT), ascorbato peroxidase (APX), guaiacol peroxidase (GPX) e superóxido dismutase (SOO), quer na raiz quer na parte aérea. Foi observado um aumento significativo (versus controlo) na peroxidação lipídica e actividade enzimática da CATe APX na parte aérea da B. juncea, N. tabacum e S. nigrum para os níveis de contaminação mais elevados, 15 e/ou 35 mg Cd kg-1 A B. juncea apresentou maior sensibilidade na resposta da GPX, para todas as concentrações de Cd no solo. A peroxidação lipídica e a actividade da CAT foram superiores na parte aérea em relação à raiz para todas as plantas em todas as contaminações de Cd presentes no solo. A actividade da SOO não apresentou respostas consistentes para nenhuma das plantas. ABSTRACT: Remediation of sites contaminated with heavy metals using hyper accumulators seems a promising alternative to engineering approaches. ln this work, we compared cadmium (Cd) accumulation and tolerance (based on responses to oxidative stress) in three different species, Brassica juncea (L) Czem., Nicotiana tabacum L. and Solanum nigrum L., described in the literature as very tolerant or even as hyper accumulators. The plants were grown in soil spiked with different Cd concentrations (O- 35 mg kg- 1) over a period of 90 days. The translocation factor (TF), used to measure the effectiveness of translocating Cd from roots to shoots, depended greatly on the species. N. tabacum was the plant which exhibited the highest TF values. lt was the only plant under study that fulfilled the conditions of a hyper accumulator for all levels of soil contamination. On the other hand, S. nigrum presented the highest Cd concentration in plant tissues, with TF > 1 in the presence of 5 mg Cd kg-1 of soil. Although B. juncea had presented the lowest TF and Cd concentrations, it was the only plant with TF values increasing with the level of cadmium. Oxidative stress in plants was evaluated by lipid peroxidation and activities of catalase (CAT), ascorbate peroxidase (APX), guaiacol peroxidase (GPX) and superoxide dismutase (SOO), both in roots and shoots. A significant enhancement (versus control) on lipid peroxidation and enzymatic activity of CAT and APX in shoots of B. juncea, N. tabacum and S. nigrum was observed for the highest levels of Cd in soil, 15 and/or 35 mg Cd kg-1. B. juncea presented the most sensitive response of GPX, for all levels of Cd in soil. Lipid peroxidation and CAT activity were greater in shoots than in roots for all plants and soil Cd concentrations. SOO activity did not present consistent trends for any plant.

SISTEMAS DE INFORMACIÓN GEOGRÁFICA COMO HERRAMIENTA PARA EVALUAR LA APORTACIÓN ANTROPICA DE MERCURIO EN SUELOS

Este trabajo evalúa el contendido y la variabilidad espacial de mercurio en suelos agrícolas de Islas Baleares y Canarias utilizando técnicas integradas en los sistemas de información geográfica. El propósito de este estudio ha sido valorar el contenido y distribución del mercurio en el suelo y distinguir la contribución considerada como natural, y procedente del aporte de la roca de origen, de la inducida por actividades humanas, considerada como contaminante. El SIG se muestra comouna tecnología capaz de localizar fuentes de contaminación y proporcionar el alcance de éstos. Los mapas generados con la relación de Hg_suelo/Hg_roca han permitido cuantificar las entradas de este metal en el suelo y evaluar el enriquecimiento de mercurio en el mismo. Valores excesivamente elevados encontrados en un área de la Isla de Mallorca son atribuibles a las emisiones de una planta eléctrica de carbón cercana.PALABRAS CLAVE: Análisis espacial, SIG, geostadística, mercurio, contaminación de suelos.ABSTRACTThis study assesses Hg concentration and the spatial variability of mercury in agricultural soils of the Balearic and Canary Islands using integrated techniques of geographic information systems. The purpose of this study was to characterize in quantitative terms the mercury concentrations and to distinguish “natural” mercury contribution from that of human-induced contamination. GIS is shown to be technologically capable of locating sources of pollution and assessing their scope. The top soil/rock mercury content maps showed a high level of mercury in the same areas. Excessively high Hg values found in an area of the island of Mallorca are attributable to emissions from a coalfired power plant nearby.KEYWORDS: Spatial analysis, GIS, geostatistic, mercury, soil contamination

Modelling the fate of chromated copper arsenate in a sandy soil

A pulse of chromated copper arsenate (CCA, a timber preservative) was applied in irrigation water to an undisturbed field soil in a laboratory column. Concentrations of various elements in the leachate from the column were measured during the experiment. Also, the remnants within the soil were measured at the end of the experiment. The geochemical modelling package, PHREEQC-2, was used to simulate the experimental data. Processes included in the CCA transport modelling were advection, dispersion, non-specific adsorption (cation exchange) and specific adsorption by clay minerals and organic matter, as well as other possible chemical reactions such as precipitation/dissolution. The modelling effort highlighted the possible complexities in CCA transport and reaction experiments. For example, the uneven dosing of CCA as well as incomplete knowledge of the soil properties resulted in simulations that gave only partial, although reasonable, agreement with the experimental data. Both the experimental data and simulations show that As and Cu are strongly adsorbed and therefore, will mostly remain at the top of the soil profile, with a small proportion appearing in leachate. On the other hand, Cr is more mobile and thus it is present in the soil column leachate. Further simulations show that both the quantity of CCA added to the soil and the pH of the irrigation water will influence CCA transport. Simulations suggest that application of larger doses of CCA to the soil will result in higher leachate concentrations, especially for Cu and As. Irrigation water with a lower pH will dramatically increase leaching of Cu. These results indicate that acidic rainfall or significant accidental spillage of CCA will increase the risk of groundwater pollution.

Influence of hydrocarbon contamination on clay soil microstructure

Microstructural (fabric, forces and composition) changes due to hydrocarbon contamination in a clay soil were studied using Scanning Electron Microscope (micro-fabric analysis), Atomic Force Microscope (forces measurement) and sedimentation bench test (particle size measurements). The non-polluted and polluted glacial till from north-eastern Poland (area of a fuel terminal) were used for the study. Electrostatic repelling forces for the polluted sample were much lower than for the non-polluted sample. In comparison to non-polluted sample, the polluted sample exhibited lower electric charge, attractive forces on approach and strong adhesion on retrieve. The results of the sedimentation tests indicate that clay particles form larger aggregates and settle out of the suspension rapidly in diesel oil. In non-polluted soil, the fabric is strongly aggregated – densely packed, dominate the face-to-face and edge-to-edge types of contacts, clay film tightly adheres to the surface of larger grains and interparticle pores are more common. In polluted soil, the clay matrix is less aggregated – loosely packed, dominate the edge-to-face types of contacts and inter-micro-aggregate pores are more frequent. Substantial differences were observed in the morphometric and geometrical parameters of pore space. The polluted soil micro-fabric proved to be more isotropic and less oriented than in non-polluted soil. The polluted soil, in which electrostatic forces were suppressed by hydrocarbon interaction, displays more open porosity and larger voids than non-polluted soil, which is characterized by occurrence of the strong electrostatic interaction between clay particles.

Bioavailability of zinc and copper in biosolids compared to their soluble salts.

For essential elements, such as copper (Cu) and zinc (Zn), the bioavailability in biosolids is important from a nutrient release and a potential contamination perspective. Most ecotoxicity studies are done using metal salts and it has been argued that the bioavailability of metals in biosolids can be different to that of metal salts. We compared the bioavailability of Cu and Zn in biosolids with those of metal salts in the same soils using twelve Australian field trials. Three different measures of bioavailability were assessed: soil solution extraction, CaCl2 extractable fractions and plant uptake. The results showed that bioavailability for Zn was similar in biosolid and salt treatments. For Cu, the results were inconclusive due to strong Cu homeostasis in plants and dissolved organic matter interference in extractable measures. We therefore recommend using isotope dilution methods to assess differences in Cu availability between biosolid and salt treatments.

Responses of Scots pine to nickel and copper exposure and herbivory

The goal of this thesis was to examine the ecophysiological responses of Scots pine (Pinus sylvestris L.), with an emphasis on the oxidative enzyme peroxidase and plant phenolics to environmental stresses like elevated levels of nickel (Ni) and copper (Cu), and herbivory. The effects of Ni and Cu were studied in a gradient survey at a sulphur dioxide contaminated site in the Kola Peninsula, and with experiments in which seedlings were exposed to Ni mist or to Ni and Cu amended into the soil. In addition, experimental Ni exposure was combined with disturbance of the natural lichen cover of the forest ground layer. Pine sawfly attack was simulated in the early season defoliation experiment, in which mature Scots pine were defoliated (100 %) during two successive years in a dry, nutrient-poor Scots pine stand. In addition, the effect of previous defoliation on the growth of sawfly (Diprion pini L.) larvae was studied. Apoplastic peroxidase activity was elevated in the needles of pine in a Ni- , Cu- and SO2- polluted environment, which indicated an increased oxidative stress. Increased foliar peroxidase activity due to Ni contamination was shown in the experiment, in which Ni was added as mist. No such response was found in peroxidase acitivity of the roots exposed to elevated Ni and/or Cu in the soil. Elevated Ni in the soil increased the concentration of foliar condensed tannins, which are able to bind heavy metals in the cells. Addition of low levels of Ni in the soil appeared to benefit pine seedlings, which was seen as promoted shoot growth and better condition of the roots. Wet Ni deposition of 2000 mg m-2 reduced growth and survival of pine seedlings, whereas deposition levels 200 mg m-2 or 20 mg m-2 caused no effects in a 2-y lasting experiment. The lichen mat on the forest floor did not act as an effective buffer against the adverse impacts of heavy metals on pine seedlings. However, some evidence was found indicating that soil microbes profited from the lichen mat. Artificial defoliation increased peroxidase activity in the Scots pine needles. In addition, defoliation decreased nitrogen, diamine putrescine and glucose concentrations in the needles and increased the concentrations of several phenolic compounds, starch and sucrose. Previous artificial defoliation led to poor growth of sawfly larvae reared on the pines, suggesting delayed induced resistance in Scots pine. However, there was no consistent relationship between inducibility (proportional increase in a compound following defoliation) and adverse effects on the growth of pine sawfly larvae. The observed inducible responses in needle phenolics due to previous defoliation thus appear to represent non-specific responses against sawflies.

Mechanistic evaluation of mitigation of petroleum hydrocarbon contamination by soil medium

Present in situ chemical treatment technologies for mitigation of petroleum hydrocarbon contamination are in the developmental stage or being tested. To devise efficient strategies for restricting the movement of petroleum hydrocarbon (PHC) molecules in the contaminated soil, it is proposed to utilize the sorption–interaction relationships between the petroleum contaminants and the soil substrate. The basic questions addressed in this paper are as follows (i) What are the prominent chemical constituents of the various petroleum fractions that interact with the soil substrate? (ii) What are the functional groups of a soil that interact with the contaminants? (iii) What are the bonding mechanisms possible between the soil functional groups and the PHC contaminants? (iv) What are the consequent changes brought about the soil physical properties on interaction with PHC's? (v) What are the factors influencing the interactions between PHC molecules and clay particles of the soil substrate? (vi) What is the possibility of improving the soil's attenuation ability for PHC's? The development of answers to the basic questions reveal that petroleum hydrocarbons comprise a mixture of nonpolar alkanes and aromatic and polycyclic hydrocarbons, that have limited solubility in water. The bonding mechanism between the nonpolar PHC's and the clay surface is by way of van der Waals attraction. The adsorption of the nonpolar hydrocarbons by the clay surface occurs only when their (i.e., the hydrocarbon molecules) solubility in water is exceeded and the hydrocarbons exist in the micellar form. Dilute solutions of hydrocarbons in water, i.e., concentrations of hydrocarbons at or below the solubility limit, have no effect on the hydraulic conductivity of clay soils. Permeation with pure hydrocarbons invariably influences the clay hydraulic conductivity. To improve the attenuation ability of soils towards PHC's, it is proposed to coat the soil surface with "ultra" heavy organic polymers. Adsorption of organic polymers by the clay surface may change the surface properties of the soil from highly hydrophilic (having affinity for water molecules) to organophilic (having affinity for organic molecules). The organic polymers attached to the clay surface are expected to attenuate the PHC molecules by van der Waals attraction, by hydrogen bonding, and also by adsorption into interlayer space in the case of soils containing swelling clays.

Cadmium leachability and microbial population dynamics in a stabilized and bioaugmented model contaminated soil

This article presents a laboratory study on the consequences of the application of combined soil stabilization and bioaugmentation in the remediation of a model contaminated soil. Stabilization and bioaugmentation are two techniques commonly applied independently for the remediation of heavy metal and organic contamination respectively. However, for a cocktail of contaminants combined treatments are currently being considered. The model soil was contaminated with a cocktail of organics and heavy metals based on the soil and contaminant conditions in a real contaminated site. The soil stabilization treatment was applied using either zeolite or green waste compost as additives and a commercially available hydrocarbon degrading microbial consortium was used for the bioaugmentation treatment. The effects of stabilization with or without bioaugmentation on the leachability of cadmium and copper was observed using an EU batch leaching test procedure and a flow-through column leaching test, both using deionized water at a pH of 5.6. In addition, the population of hydrocarbon degrading microorganisms was monitored using a modified plate count procedure in cases where bioaugmentation was applied. It was found that while the stabilization treatment reduced the metal leachability by up to 60%, the bioaugmentation treatment increased it by up to 100% Microbial survival was also higher in the stabilized soil samples.