Remoção de carbono orgânico dissolvido de águas filtradas com tratamento complementar por pré-oxidação com ozônio e adsorção em carvão ativado / Removal of dissolved organic carbon in filtered water complemented with treatment by pre-oxidation with ozone and adsorption on activated carbon

Resumo Este trabalho teve como objetivo avaliar as remoções de carbono orgânico dissolvido presente em águas filtradas de estação de tratamento de água com tratamento complementar por pré-oxidação com ozônio e adsorção em carvão ativado granular. Para o estudo de adsorção foi utilizado o método de ensaio rápido em coluna de escala reduzida, com carvão ativado produzido de cascas de coco. Realizou-se a comparação entre as curvas de ruptura para os ensaios com e sem aplicação de ozônio. Os resultados mostraram reduções nas concentrações de carbono orgânico dissolvido no início dos ensaios e após a passagem da água com e sem pré-ozonização pelas colunas ensaio rápido em coluna de escala reduzida seguida de incrementos progressivos das concentrações à medida que se aumentou o volume de leitos tratados. Na fase final dos ensaios, os aumentos de volume de leitos tratados não causaram mudanças significativas nas concentrações efluentes de carbono orgânico dissolvido. O mesmo comportamento foi observado com relação à absorção em radiação ultravioleta a 254 nm. O uso de ozônio previamente à adsorção em carvão ativado granular, usando o método ensaio rápido em coluna de escala reduzida, resultou em maiores reduções na absorbância da luz ultravioleta em 254 nm do que nas concentrações de carbono orgânico dissolvido. As absorbâncias específicas à radiação ultravioleta das amostras ozonizadas foram menores do que as que não receberam ozônio.

Abstract The objective of this study was to evaluate the removal of dissolved organic carbon in filtered water followed by pre-oxidation with ozone and adsorption on granular activated carbon. The rapid small-scale column test was used for the adsorption essays with activated carbon produced from coconut shells. A comparison was made between the breakthrough curves for tests performed with and without pre-oxidation with ozone. The results showed reductions in dissolved organic carbon concentrations after initial passage of water with and without ozone through the rapid small-scale column test column, followed by progressive increases in concentrations along with the number of the bed volumes. In the final phase of the tests, increases in bed volumes did not cause significative changes in effluent dissolved organic carbon concentrations. The same behavior was also observed with respect to ultra-violet absorbance at 254 nm. The use of ozone prior to adsorption on GAC, using the ERCER method, caused greater reductions on UV254 absorbance than in concentrations of dissolved organic carbon. The specific ultraviolet absorbance values of samples that received ozone were lower than those that were not ozonized.

Removal of Transition Metals from Contaminated Aquifers by PRB Technology: Performance Comparison among Reactive Materials.

The most common reactive material used for the construction of a permeable reactive barrier (PRB) is zero valent iron (ZVI), however, its processing can generate corrosive effects that reduce the efficiency of the barrier. The present study makes a major contribution to understanding new reactive materials as natural and synthetic, easy to obtain, economical and environmentally friendly as possible substitutes for the traditional ZHV to be used as filters in the removal of three transition metals (Zn, Cu, Cd). To assess the ability to remove these pollutants, a series of batch and column tests were carried out at laboratory scale with these materials. Through BACH tests, four of seven substances with a removal percentage higher than 99% were prioritized (cabuya, natural clinoptilolite zeolites, sodium mordenite and mordenite). From this group of substances, column tests were performed where it is evidenced that cabuya fiber presents the lowest absorption time (≈189 h) while natural zeolite mordenite shows the highest time (≈833 h). The latter being the best option for the PRB design. The experimental values were also reproduced by the RETRASO code; through this program, the trend between the observed and simulated values with respect to the best reactive substance was corroborated.

Remoção do 2,4-D em amostras de águas pela adsorção em leitos fixos de carvão ativado granular em escala reduzida / Removal of 2,4-D in water samples by adsorption in fixed beds of granular activated carbon on reduced scale

RESUMO O objetivo deste trabalho foi avaliar, por meio dos testes rápidos de coluna em escala reduzida, a capacidade de adsorção do carvão ativado granular (CAG) na remoção do ácido 2,4-diclorofenoxiacético (2,4-D) em amostras de água ultrapura e de água filtrada proveniente de estação de tratamento de água. Os valores da capacidade de adsorção obtidos a partir de amostras de água ultrapura foram 67% superiores aos obtidos para água com presença de matéria orgânica natural (MON). A MON influenciou fortemente a remoção de 2,4-D competindo pelos sítios de adsorção do carvão ativado e diminuiu a capacidade de adsorção para 7,43 mg 2,4-D por grama de CAG. Para a concentração de 2,4-D no afluente igual a 7089 ± 104 µg.L-1 e relação volumeágua/volumeCAG estimado em 766, foi possível produzir água com concentração de 2,4-D inferior a 30 µg.L-1, como recomendado pela Portaria Brasileira de Potabilidade de Água, do Ministério da Saúde (Portaria MS nº 2.914/2011).

ABSTRACT The aim of this study was to assess by means of rapid tests of small-scale column the adsorption capacity of granular activated carbon (GAC) for removal of 2,4-dichlorophenoxyacetic acid (2,4-D) from samples of ultrapure water and filtered water from a water treatment plant. The adsorption capacities values obtained from distilled water samples were 67% higher than those obtained for water having natural organic matter (NOM). NOM strongly influenced the removal of 2,4-D, competing for GAC adsorption sites, and decreasing its adsorption capacity to 7 mg 2,4-D g-1 CAG. For 2,4-D concentration of 7089 ± 104 µg L-1 and the water treated volume/GAC volume at 766, it was possible to produce treated water with 2,4-D concentration less than 30 µg L-1 as recommended by Brazilian Drinking Water Legislation of the Ministry of Health (Portaria MS 2914/2011).

Biostimulation and rainfall infiltration: influence on retention of biodiesel in residual clayey soil.

This study investigates the retention of biodiesel in residual clayey soil during biostimulation by nutrients (nitrogen, phosphorus, and potassium) under conditions of rainfall infiltration. Several column tests were conducted in a laboratory under different void ratios (1.14, 1.24, and 1.34), varying moisture contents (15, 25, and 35%), and in both the presence and absence of biostimulation. The volume of biodiesel (which was equivalent to the volume of voids in the soil) was placed atop the soil and allowed to percolate for a period of 15 days. The soil was subjected to different rainfall infiltration conditions (0.30 or 60 mm). The greatest reductions in residual contaminants occurred after 60 mm of rain simulation, at values of up to 74% less than in samples with the same conditions but no precipitation. However, the residual contamination decay rate was greater with 0-30 mm (0.29 g/mm) of precipitation than with 30-60 mm (0.075 g/mm). Statistical assessment revealed that increased moisture and the presence of nutrients were the factors with the most powerful effect on contaminant retention in the soil. The residual contaminant level was 21 g/kg at a moisture content of 15% and no precipitation, decreasing to 12 g/kg at 35% moisture and no precipitation. Accordingly, it is possible to conclude that biostimulation and rainfall infiltration conditions can decrease the retention of contaminants in soil and allow a greater leaching or spreading of the contamination. All of these phenomena are worthy of careful examination for the in situ bioremediation of organic contamination. HIGHLIGHTS: • The higher moisture in the soil, due to a high initial moisture content and/or infiltration of rainfall, can reduce contaminant retention, • The use of biostimulation through the addition of nutrients to accelerate the biodegradation of toxic organic contaminants may induce inadvertent undesirable interactions between the soil and the contaminant. • When adopting biostimulation for bioremediation, the effects of rainfall should be addressed; ideally, it should be prevented from entering the affected site, in order to avoid increased contaminant leaching and potential spreading.

Predição da performance de carvão ativado granular para remoção de herbicidas com ensaios em coluna de escala reduzida / Prediction of granular activated carbon performance in removing herbicides with rapid small-scale column tests

RESUMO: Na região de Ribeirão Preto está localizado um dos polos produtores da cana-de-açúcar, com vasta área cultivada e uso intensivo de herbicidas, tais como o diuron e a hexazinona, os quais possuem elevado potencial de contaminação em águas superficiais e subterrâneas. Diversas tecnologias podem ser utilizadas para remover esses microcontaminantes da água, em função de, neste caso, não ser eficiente a técnica de tratamento em ciclo completo (ou convencional). Neste trabalho, estudou-se o desempenho do carvão ativado granular na remoção destes herbicidas. A água de estudo foi preparada em laboratório e fortificada com diuron e hexazinona. Foi construída e operada uma instalação piloto com colunas de adsorção em carvão ativado granular, cujos resultados obtidos mostraram que a difusividade intrapartícula predominante entre o carvão e os herbicidas diuron e hexazinona pode ser considerada constante, em relação ao tamanho do grão de carvão ativado. Eles também possibilitaram a validação do método de ensaios rápidos em coluna de carvão ativado em escala reduzida, com vista à predição do tempo para ruptura de um filtro de carvão ativado granular em escala real.

ABSTRACT: Ribeirão Preto has one of the producer poles of sugarcane, with a vast sugarcane plantation area and intensive use of herbicides, especially diuron and hexazinone, which have high potential of contaminating surface waters and groundwater. Several technologies can be used to remove these micro-contaminants from water, since the conventional treatment in complete cycle is not an efficient technique for this case. In the present study, the performance of the granular activated carbon in removing these herbicides was evaluated. The water sample was prepared in a laboratory and supplemented with diuron and hexazinone. A pilot granular activated carbon column was built and operated, and the results showed that the prevailing intra-particle diffusivity between carbon and diuron and hexazinone herbicides could be considered constant, with regard to the size of the activated carbon grain. The results obtained also enabled the validation of the rapid small-scale column test method to predict the full scale breakthrough time of a granular activated carbon filter.