Optimization of ozonation process for organic matter and ecotoxicity removal from landfill leachate by applying rotatable central composite design (RCCD).

Ozonation process was used for leachate treatment from a landfill located in Rio de Janeiro, Brazil. The influence of pH and ozone concentration on COD (Chemical Oxygen Demand), TOC (Total Organic Carbon), Absorbance at 254 nm (ABS254nm), and True color was evaluated through RCCD (Rotatable Central Composite Design) experimental design, resulting in mathematical models that were statistically analyzed in Statistica and Design Expert software. The removals obtained was up to 26.1%, 29.9%, 56.9%, and 97.9% for COD ([COD]0=3,323 mg/L), TOC ([TOC]0=1,275 mg/L), ABS254nm (ABS0=32.2), and True color ([True color]0=3,467 mgPt-Co/L), respectively. Statistical and variance analysis of the experimental data revealed that one quadratic model obtained in Statistica was valid, ABS254nm reduction. However, by applying the Design Expert software, modified models were generated to predict the behavior of all dependent variables. Thus, the optimum point for the best response after ozonation of the landfill leachate was at the highest pH and the lowest ozone dose (9 and 2.2 mgO3/m3, respectively). Toxicity toward Allivibrio fischeri bacteria was abated at the same time that it decreased the impact of the effluent to Danio rerio fish (from 125 UT to 62 UT) on the treated leachate.

Synthesis and characterization of hydrocalumite for removal of fluoride from aqueous solutions.

Fluoride can cause some diseases to humans when ingested in large quantities and for a long time. Due to this, it is necessary to remove or reduce the amount of fluoride in effluents before release into the water bodies. This work aimed to evaluate the ability of hydrocalumites synthesized by two different methodologies and calcined hydrocalumite in reducing the content of fluoride in aqueous solutions. The materials were characterized by X-ray diffraction (XRD), X-ray fluorescence (XRF), N2 physisorption, thermogravimetric analysis (TGA), and differential thermal analysis (DTA). The removal capacity of fluoride ions ranged from 14.9 to 189.6 mg F- g-1. The removal mechanisms by hydrocalumites were ion exchange and adsorption at low concentrations, while at high concentrations were adsorption and precipitation of calcium fluoride. In relation to the use of calcined hydrocalumite, the removal mechanisms were ion exchange and reconstruction of structure (memory effect) in low concentrations. By the adsorption tests, it was observed that the results fit better the Langmuir isotherm model.

Evaluation of the acute effects of chemical additives on the toxicity of a synthetic oilfield produced water.

This study evaluated the acute effects of nine different production chemicals typically employed in oil exploration on the toxicity of a synthetic produced water (PW). Bioassays with the Microtox® System were performed to monitor changes in the level of light emission of the marine luminescent bacteria Vibrio fischeri during exposure to the samples. The results show that synthetic PW is moderately toxic to these organisms, and the addition of oilfield chemicals significantly increases its toxicity. For most of the additives tested, the toxicity of the aqueous phase following partitioning against crude oil was not strongly altered by the presence of these chemicals. Synergistic effects occurred in the three different mixtures investigated. Among the additives studied, biocide, corrosion inhibitor, H2S scavenger, and surfactant were the most toxic for V. fischeri. Furthermore, the surfactant has been identified as the possible source of the acute toxicity observed.

Evaluation of humic substances removal from leachates originating from solid waste landfills in Rio de Janeiro State, Brazil.

This study aimed to evaluate the use of coagulation/flocculation and Fenton processes for the removal of the recalcitrant component, in particular humic substances, from two different leachates generated in the Gericinó and Gramacho landfills in Rio de Janeiro State (Brazil). A coagulation/flocculation process, using FeCl3·6H2O as the coagulant, was applied to the two leachate samples. In the case of the leachate from Gericinó landfill, the treatment removed 93% of color, 71% of TOC, 69% of COD, 76% of HS, 73% of humic acids (HA) and 82% of fulvic acids (FA). In addition, there was a 75% reduction in the absorbance at 254 nm, using 3,000 mg L-1 of coagulant. In the case of the leachate from Gramacho landfill, the treatment removed 91% of color, 69% of TOC, 68% of COD, 77% of HS, 75% of HA and 80% of FA. In addition, there was a 70% reduction in the absorbance at 254 nm using the same concentration of coagulant (3,000 mg L-1). The Fenton processes, using FeSO4·7H2O and H2O2 in a ratio of 1:5, were also applied to the two leachate samples. In the case of the Gericinó leachate, the Fenton treatment removed 95% of color, 75% of TOC, 68% of COD, 82% of HS, 77% of HA and 93% of FA. In addition, there was a 93% reduction in the absorbance at 254 nm. In the case of the Gramacho leachate, the Fenton treatment removed 93% of color, 73% of TOC, 71% of COD, 81% of HS, 76% of HA, 90% of FA, and there was an 84% reduction in the absorbance at 254 nm. The results of humic substances, color, organic matter and aromatic organic matter (absorbance at 254 nm) demonstrate that the coagulation/flocculation and Fenton processes were efficient in the removal of recalcitrant organic matter from landfill leachates.

Toxicity identification and evaluation (TIE) of a petroleum refinery wastewater.

Petroleum refineries generate large amounts of wastewaters, which can have acute/chronic toxicity toward aquatic organisms. Previous studies have shown that many contaminants can be responsible for this toxicity, among them ammonia, sulfide, cyanide, phenols and hydrocarbons. In the study reported herein, the cause of the chronic toxicity of a biotreated petroleum refinery wastewater was investigated by applying the TIE methodology using the microcrustacean Ceriodaphnia dubia. Five samples were analyzed, and the results suggest that copper is the primary toxicant, showing a strong correlation with wastewater toxicity in Phase III. Other metal contaminants, such as zinc and nickel, are present in the samples at toxic concentrations and these may also contribute (to a lesser degree) toward the toxicity. In the case of one sample, the toxicity was attributed to polycyclic aromatic hydrocarbons (PAHs), possibly benzo(a)pyrene, which was present at a concentration toxic to C. dubia. Although the values for the physicochemical parameters of the samples were below Brazilian environmental regulation limits (CONAMA 430), this was not sufficient to prevent chronic toxicity toward aquatic life, indicating that these limits are relatively high.

Advanced oxidative processes and membrane separation for micropollutant removal from biotreated domestic wastewater.

The presence of micropollutants in sewage is already widely known, as well as the effects caused by natural and synthetic hormones. Thus, it is necessary to apply treatments to remove them from water systems, such as advanced oxidation processes (AOPs) and membrane separation processes, which can oxidize and remove high concentrations of organic compounds. This work investigated the removal of 17ß-estradiol (E2), 17α-ethinylestradiol (EE2), and estriol (E3) from biotreated sewage. Reverse osmosis processes were conducted at three recoveries (50, 60, and 70 %). For E2 and EE2, the removals were affected by the recovery. The best results for RO were as follows: the E2 compound removal was 89 % for 60 % recovery and the EE2 compound removal was 57 % for 50 % recovery. The RO recovery did not impact the E3 removal. It was concluded that the interaction between the evaluated estrogens, and the membrane was the major factor for the hormone separation. The AOP treatment using H2O2/UV was carried out in two sampling campaigns. First, we evaluated the variation of UV doses (24.48, 73.44, 122.4, and 244.8 kJ m-2) with 18.8 mg L-1 of H2O2 in the reaction. EE2 showed considerable removals (around 70 %). In order to optimize the results, an experimental design was applied. The best result was obtained with higher UV dose (122.4 kJ m-2) and lower H2O2 concentration (4 mg L-1), achieving removal of 91 % for E3 and 100 % for E2 and EE2.

Removal of ammonia nitrogen from leachate of Muribeca municipal solid waste landfill, Pernambuco, Brazil, using natural zeolite as part of a biochemical system.

The inadequate disposal of leachate is one of the key factors in the environmental impact of urban solid waste landfills in Brazil. Among the compounds present in the leachates from Brazilian landfills, ammonia nitrogen is notable for its high concentrations. The purpose of this study was to assess the efficiency of a permeable reactive barrier filled with a natural zeolite, which is part of a biochemical system for the tertiary treatment of the leachate from Muribeca Municipal Solid Waste Landfill in Pernambuco, Brazil, to reduce its ammonia nitrogen concentration. This investigation initially consisted of kinetic studies and batch equilibrium tests on the natural zeolite to construct the sorption isotherms, which showed a high sorption capacity, with an average of 12.4 mg NH4+.L(-1), a value close to the sorption rates found for the aqueous ammonium chloride solution. A permeable reactive barrier consisting of natural zeolite, as simulated by the column test, was efficient in removing the ammonia nitrogen present in the leachate pretreated with calcium hydroxide. Nevertheless, the regenerated zeolite did not satisfactorily maintain the sorption properties of the natural zeolite, and an analysis of their cation-exchange properties showed a reduced capacity of 54 meq per 100 g for the regenerated zeolite compared to 150 meq per 100 g for the natural zeolite.

Removal of COD from a stabilized landfill leachate by physicochemical and advanced oxidative process.

This work investigated the effectiveness of a physicochemical and oxidative process for the removal of chemical oxygen demand (COD) from stabilized landfill leachates. The application of these technologies for landfill leachate treatment greatly depends on the optimal operating conditions for a specific leachate. Coagulation-flocculation followed by H2O2, Fenton and photo-Fenton processes was evaluated. Advanced oxidation processes were evaluated in the raw leachate and the leachate pretreated by coagulation-flocculation. Via the coagulation process, at 30 sec and a stirring speed of 150 rpm followed by flocculation and settling steps, 53% COD was removed at an optimal dose of 1400 mg L(-1) and pH 4.0. Moreover, from the POA evaluated, the Fenton process was determined to be the most effective process for removing COD from the leachate pretreated by coagulation-flocculation, reaching 83.3% COD removal with 1330 mg L(-1) of H2O2 and 266 mg L(-1) of Fe(2+). The photo-Fenton process applied directly to the raw effluent was effective for the removal of COD; a 75% reduction in COD was observed in tests using 2720 mg L(-1) of H2O2 and 544 mg L(-1) of Fe(2+). Due to the variability in the composition of the Gramacho landfill leachate, the combination of coagulation-flocculation and the Fenton process is an effective technology for reducing the COD in samples of this leachate.

Removal of boron from oilfield wastewater via adsorption with synthetic layered double hydroxides.

Hydrotalcite is a layered double hydroxide (LDH) consisting of brucite-like sheets of metal ions (Mg-Al). In this work, hydrotalcites were synthesized, and boron removal from oilfield wastewater was evaluated. LDHs were synthesized using the co-precipitation method. The calcined products (CLDHs) were obtained by heating at 500°C and characterized using X-ray diffraction, X-ray fluorescence, thermogravimetric analysis and the specific surface area (BET). The affinity of LDHs for borate ions was evaluated for calcined and uncalcined LDHs as a function of contact time, initial pH of the oilfield wastewater (pH ∼ 9) and the LDH surface area. The tests were conducted at room temperature (approximately 25ºC). The results indicated that 10 min were needed to reach a state of equilibrium during boron removal for calcined LDHs due to the high surface area (202.3 m(2) g(-1)) regardless of the initial pH of the oilfield wastewater, which resulted from the high buffering capacity of the LDHs. The adsorption capacity increased as the adsorbents levels increased for the range studied. After treatment of the oilfield wastewater containing 30 mg L(-1) of boron with Mg-Al-CO3-LDHs, the final concentration of boron was within the discharge limit set by current Brazilian environmental legislation, which is 5 mg L(-1). Pseudo-first-order and pseudo-second-order kinetic models were tested, and the latter was found to fit the experimental data better. Isotherms for boron adsorption by CLDHs were well described using the Langmuir and Freundlich equations.