Combined reverse osmosis and UV/H2O2 treatment of aqueous solutions of bisphenol A and 17α-ethinylestradiol: assessment of estrogenic activity.

Bisphenol-A (BPA) and 17α-ethinylestradiol (EE2) are considered endocrine disrupting compounds (EDC) and they may be harmful to the normal functioning of endocrine systems of humans and animals. Moreover, the presence of these compounds in superficial and groundwater may represent serious risks, even in low concentrations like ng·L-1. The objectives of this study were to remove BPA and EE2 from solutions containing a mixture of these compounds in ultrapure water at low concentrations through reverse osmosis (RO) membrane combined with a UV/H2O2 process. Furthermore, to assess the estrogenic activity reduction after such treatments, in vitro recombinant yeast-estrogen screen (YES) assay was used. The removal efficiencies of target micropollutants increased with the increase of H2O2 dosage. For RO permeate stream, they enhanced from 91% to 96% for EE2 and from 76% to 90% for BPA while, for the concentrate stream, from 70% to 81% for EE2 and 41% to 84% for BPA as the H2O2 concentration were increased from 100 to 1000 µg·L-1. The OH radicals' generation was the dominant factor in the degradation of EDC during the UV/H2O2 treatment since the photolysis itself was not enough to degrade BPA or EE2. The estrogenic activity reduction after UV/H2O2 treatment was high, ranging from 92% to 98% for the permeate stream and from 50% to 93% for the concentrate stream. The EE2 was responsible for the whole observed estrogenic activity since BPA does not present estrogenicity, by in vitro YES assay, in the concentrations observed.

Assessment of fouling mechanisms on reverse osmosis (RO) membrane during permeation of 17α-ethinylestradiol (EE2) solutions.

Fouling mechanisms are mainly caused by the deposition of organic compounds that reduce the removal efficiency on reverse osmosis (RO) membranes. It can be described by mathematical models. The aim of this study was to evaluate the membrane fouling and rejection mechanisms when aqueous solutions containing 17α-ethinylestradiol (EE2) in different concentrations are permeated at 5 and 10 bar in a bench-scale dead-end RO system. Adsorption tests were performed and the fouling mechanism was assessed by Hermia's model for solutions of EE2 at concentrations typically found in the environment (µg L-1). Fourier transform infrared spectroscopy (FTIR) has indicated the presence of EE2 on the fouled membrane surface. Membrane rejection of EE2 ranged from 90% to 98% and the main rejection mechanism was size exclusion at all experimental conditions. However, for the higher concentration of EE2 permeated at 5 and 10 bar, adsorption of 7 and 32 mg m-2, respectively, also took place. The rejection was influenced by fouling and concentration polarisation. Fouled membranes present higher rejection of hydrophobic neutral compounds and the concentration polarisation reduces rejection. Hermia's model demonstrated that the permeation values fitted better the standard blocking filtration and cake filtration equations for describing fouling mechanism. This study showed that fouling also occurs in the TFC RO membrane after permeation of EE2, which corroborates with studies using other pollutants.

Biodegradation of natural and synthetic endocrine-disrupting chemicals by aerobic granular sludge reactor: Evaluating estrogenic activity and estrogens fate.

In this study, the biodegradation of endocrine-disrupting chemicals (EDCs) (namely the natural and synthetic estrogens 17ß-estradiol (E2) and 17α-ethinylestradiol (EE2), respectively) was assessed in an aerobic granular sludge (AGS) sequencing batch reactor (SBR) treating simulated domestic sewage. To better understand the fate of these compounds, their concentrations were determined in both liquid and solid (biomass) samples. Throughout the operation of the reactor, subjected to alternating anaerobic and aerated conditions, the removal of the hormones, both present in the influent at a concentration of 20 µg L-1, amounted to 99% (for E2) and 93% (for EE2), with the latter showing higher resistance to biodegradation. Through yeast estrogen screen assays, an average moderate residual estrogenic activity (0.09 µg L-1 EQ-E2) was found in the samples analysed. E2 and EE2 profiles over the SBR cycle suggest a rapid initial adsorption of these compounds on the granular biomass occurring anaerobically, followed by biodegradation under aeration. A possible sequence of steps for the removal of the micropollutants, including the key microbial players, was proposed. Besides the good capability of the AGS on EDCs removal, the results revealed high removal efficiencies (>90%) of COD, ammonium and phosphate. Most of the incoming organics (>80%) were consumed under anaerobic conditions, when phosphate was released (75.2 mgP L-1). Nitrification and phosphate uptake took place along the aeration phase, with effluent ammonium and phosphate levels around 2 mg L-1. Although nitrite accumulation took place over the cycle, nitrate consisted of the main oxidized nitrogen form in the effluent. The specific ammonium and phosphate uptake rates attained in the SBR were found to be 3.3 mgNH4+-N gVSS-1.h-1 and 6.7 mgPO43--P gVSS-1 h-1, respectively, while the specific denitrification rate corresponded to 1.0 mgNOx--N gVSS-1 h-1.

Treatment of Bisphenol A (BPA) in water using UV/H2O2 and reverse osmosis (RO) membranes: assessment of estrogenic activity and membrane adsorption.

Removal of an endocrine disrupting compound, Bisphenol A (BPA), from water was investigated using two treatment processes, UV/H2O2 advanced oxidation (AOP) and reverse osmosis (membrane separation). Furthermore, changes in estrogenic activity using in vitro yeast estrogen screen assay as well as the adsorption of BPA by the membrane surface were evaluated. The best UV/H2O2 performance was obtained using the highest established values of all parameters, reaching 48% BPA removal. Within the investigated conditions of the AOP, when lower doses of UV were used, a higher removal efficiency was achieved at a higher initial concentration of BPA. However, the same behavior was not observed for the highest UV dose, in which the removal efficiency was not dependent on BPA initial concentration. In both cases, removal efficiency increased as H2O2 concentration increased. The formation of estrogenic by-products was observed in UV/H2O2. The membrane rejection efficiency varied from 60% to 84% and all experiments showed adsorption of BPA by the membrane surface. The RO membrane showed a greater BPA removal efficiency for samples containing 10 µg·L-1 than UV/H2O2 at the evaluated treatment conditions.

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.

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.

Treatment of an industrial stream containing vinylcyclohexene by the H2O2/UV process.

Petrochemical industries generate wastewaters containing pollutants that can severely impact the biological treatment systems. Some streams from specific production units may contain nonbiodegradable or toxic compounds that impair the performance of the wastewater treatment plant and should be segregated and treated by specific techniques. In this work, the utilization of chemical oxidation (H2O2/UV) was investigated for removing 4-vinylcyclohexene (VCH) from a liquid stream coming from the production of hydroxylated liquid polybutadiene (HLPB). Besides VCH, this stream also contains ethanol, hydrogen peroxide, and many other organic compounds. Experiments were carried out in a small-scale photochemical reactor (0.7 L) using a 25-W low-pressure mercury vapor lamp. The photochemical reactor was operated in batch, and the reaction times were comprised between 10 and 60 min. Assays were also performed with a synthetic medium containing VCH, H2O2, and ethanol to investigate the removal of these substances in a less complex aqueous matrix. By-products formed in the reaction were identified by gas chromatography and mass spectroscopy (GC-MS). VCH was significantly removed by the oxidation process, in most assays to undetectable levels. Ethanol removal varied from 16 to 23 % depending on the reaction conditions. Acetic acid, acetaldehyde, and diols were detected as by-products of the industrial wastewater stream oxidation. A drop on the toxicity of the industrial stream was also observed in assays using the organism Artemia salina.

Assessment of combined treatment of landfill urban solid waste leachate and sewage using Danio rerio and Daphnia similis.

The co-treatment from Morro do Céu landfill leachate with domestic sewage in the Icaraí STP was monitored with regard to the behavior of toxicity of its inflows and outflow. Leachate not exceeded 1.5% in volume in the plant. The acute ecotoxicological tests showed that, although leachate is far more harmful to D. rerio (LC50 approximately = 4) and D. similis (LC50 approximately = 5) than sewage (LC50 approximately = 62; LC50 approximately = 22), statistically the mixture of leachate with sewage did not result in a more toxic inflow (LC50 approximately = 57; LC50 approximately = 12) for treatment than raw sewage. After treatment, the outflow toxicity (LC50 approximately = 76; LC50 approximately = 16) complied with the environmental laws.

Ozonation and advanced oxidation technologies to remove endocrine disrupting chemicals (EDCs) and pharmaceuticals and personal care products (PPCPs) in water effluents.

Advanced oxidation processes (AOPs) constitute a promising technology for the treatment of wastewaters containing pharmaceuticals and personal care products (PPCPs) and especially endocrine disrupting chemicals (EDCs). Data concerning the degradation of PPCPs and EDCs by means of AOPs reported during the period January 2000-May 2007 are evaluated in this work. Ozonation was the oxidation process most studied, gives the best expectatives to be applied with successful results.

Ozonation of a landfill leachate: evaluation of toxicity removal and biodegradability improvement.

This work shows an evaluation of treatments for the leachate produced at the Gramacho Municipal Landfill in Rio de Janeiro state, Brazil. This leachate has very peculiar characteristics, with a high salinity level and very low biodegradability (BOD(5)/COD of 0.05). A sequence of processes was employed in the treatment of this leachate. Initially, a physicochemical treatment was used, while the second stage consisted of application of ozone to improve the biodegradability of the leachate. The final stage comprised a biological treatment. The physical-chemical treatment led to COD and DOC removal levels of 40 and 25%, respectively, with the use of Al(2)(SO(4))(3). The sequence of treatments proposed brought good results, with an increase in the BOD(5)/COD ratio from 0.05 to 0.3 after ozonation. The toxicity tests performed using Brachydanio rerio and Poecilia vivipara showed that the toxicity of the leachate had hardly been reduced by ozonation. These results are in agreement with the fact that, despite the higher BOD(5)/COD ratio, the biological process did not present a good performance. The total average removal levels of COD and DOC achieved using the combined treatment were 73 and 63%, respectively, for an ozone dose of 3.0 gL(-1) by the leachate.