Activated carbon modifications to enhance its water treatment applications. An overview.

The main objective of this study was to list and compare the advantages and disadvantages of different methodologies to modify the surface of activated carbons (ACs) for their application as adsorbents to remove organic and inorganic pollutants from aqueous phase. These methodologies have been categorized into four broad groups: oxidation, sulfuration, ammonification, and coordinated ligand anchorage. Numerous investigations into the removal of metals from water have modified carbon surfaces to increase their content of acidic surface functional groups by using H(2)O(2), O(3) and HNO(3). Because these treatments can reduce the AC surface area, researchers are seeking alternative methods to modify and/or create surface functional groups without the undesirable effect of pore blockage. The nitrogenation or sulfuration of the AC surface can increase its basicity favoring the adsorption of organic compounds. The introduction of nitrogen or sulfur complexes on the carbon surface increases the surface polarity and, therefore, the specific interaction with polar pollutants. Different coordinated ligands have also been used to modify ACs, showing that coordinated ligand anchorage on the AC surface modifies its textural and chemical properties, but research to date has largely focused on the use of these modified materials to remove heavy metals from water by complexes formation.

Degradation of bisphenol A in water by Fe(III)/UVA and Fe(III)/polycarboxylate/UVA photocatalysis.

The photodegradation of the endocrine disrupting chemical Bisphenol A (BPA) under UVA irradiation in the presence of Fe(III) or Fe(III)-polycarboxylate systems was studied. The effect of Fe(III) concentration, aqueous pH and the presence of four carboxylic acids (oxalic, malic, tartaric and citric) were investigated. The Fe(III)/UVA system was able to effectively degrade BPA at pH 3 but failed at pH > 4. At any rate, no mineralization of BPA was achieved with the Fe(III)/UVA system. The presence of carboxylic acids greatly enhanced the BPA degradation rate because of the formation of photoactive Fe(III)-polycarboxylate complexes. Aqueous pH in the 3-7 range exerted a negative effect on the BPA degradation rate and TOC conversion in the presence of oxalic, malic and tartaric acids. Only slight effect of pH was observed in the presence of citric acid, being the BPA degradation rate significant even at pH 7.

Enhanced adsorption of metal ions onto functionalized granular activated carbons prepared from cherry stones.

Some granular activated carbons (GACs) were prepared from cherry stones (CS), an agricultural waste, by thermal methods following pyrolysis in nitrogen and subsequent activation (with air, carbon dioxide and steam) or single-step activation in steam. A GAC prepared by activation with carbon dioxide was further treated with several oxidizing agents (air, air-ozone mixture, nitric acid and hydrogen peroxide). The non-oxidized GACs produced have surface areas ranged from 508 to 901m(2)/g and show a predominantly micro- and macropores structure. Oxidation treatments, especially with nitric acid and ozone, led to the fixation of high amounts of acidic surface oxygen complexes (SOCs), thus making the carbon surface more hydrophilic. Contrary to oxidation with the other agents, the ozone treatment, at the conditions applied in this work, does not decrease the GAC surface area. Both, the non-oxidized and the oxidized GACs were used as adsorbent to study the adsorption of Cu(II) from aqueous solution. Adsorption isotherms were obtained at 25 degrees C and data were well fitted to the Langmuir equation. The results show that the Cu(II) uptake of the non-oxidized GACs is not great, but similar to that of the commercial grade Filtrasorb 400. The adsorption capacity for Cu(II) could be greatly enhanced by GAC oxidation, especially with nitric acid and ozone treatments. The larger adsorption capacity of the oxidized GACs has been attributed to oxygen functionalities (mainly carboxylic) fixed on the GAC surface, which can remove Cu(II) species from water by both ion-exchange and surface complexation mechanisms. The ozonated GAC was also evaluated for the adsorption of Co(II) species from single solute and Cu(II)-Co(II) binary mixture solutions. The functionalization of GAC by the ozone treatment improved the adsorption of both Cu(II) and Co(II) regardless of the fact that they were in single solute or binary systems.

Ozonation of activated carbons: Effect on the adsorption of selected phenolic compounds from aqueous solutions.

The impact of ozonation on textural and chemical surface characteristics of two granular activated carbons (GAC), namely F400 and AQ40, and their ability to adsorb phenol (P), p-nitrophenol (PNP), and p-chlorophenol (PCP) from aqueous solutions have been studied. The porous structure of the ozone-treated carbons remained practically unchanged with regard to the virgin GAC. However, important modifications of the chemical surface and hydrophobicity were observed from FTIR spectroscopy, pH titrations, and determination of pH(PZC). As a rule, the ozone treatment at either room temperature (i.e., about 25 degrees C) or 100 degrees C gave rise to acidic surface oxygen groups (SOG). At 25 degrees C primarily carboxylic acids were formed while a more homogeneous distribution of carboxylic, lactonic, hydroxyl, and carbonyl groups was obtained at 100 degrees C. The experimental isotherms for phenolic compounds on both GAC were analyzed using the Langmuir model. Dispersive interactions between pi electrons of the ring of the aromatics and those of the carbon basal planes were thought to be the primary forces responsible for the physical adsorption whereas oxidative coupling of phenolic compounds catalyzed by basic SOG was a major cause of irreversible adsorption. The exposure of both GAC to ozone at room temperature decreased their ability to adsorb P, PNP, and PCP. However, when ozone was applied at 100 degrees C adsorption was not prevented but in some cases (P and PNP on F400) the adsorption process was even enhanced.

Comparison between thermal and ozone regenerations of spent activated carbon exhausted with phenol.

Thermal and ozone regenerations of granular activated carbons (GAC) used in the removal of phenol from aqueous solution have been studied. The phenol isotherms for virgin GAC could be well represented by the Langmuir equation. Direct ozonation of GAC introduced large amounts of acidic surface oxygen groups, which caused a decrease in the phenol uptake. Thermogravimetric methods were used to investigate the mechanism of phenol adsorption onto virgin and ozonated carbons. Thermal regeneration was carried out at 1123K using nitrogen (pyrolysis alone) or nitrogen and carbon dioxide (pyrolysis plus oxidation). Results showed that spent carbons do not recover their adsorption characteristics when heated under inert conditions whereas carbon dioxide regeneration was effective at about 15% wt burn-off. Regeneration of GAC was also carried out with ozone as oxidizing gas at room temperature. Ozone dose and the nature of GAC have much influence on the regeneration performance. For an individual GAC there exits an optimum ozone dose for which phenol is eliminated together with most of its oxidation by-products without incurring in carbon surface chemical alterations. However, if excessive ozone is applied some acidic surface groups are formed on the GAC, thereby decreasing the adsorption capacity for phenol. Results showed that spent carbons can recover most of their adsorption characteristics and specific surface areas when regenerated through a number of adsorption-ozone regeneration cycles.

Treatment of high strength distillery wastewater (cherry stillage) by integrated aerobic biological oxidation and ozonation.

The performance of integrated aerobic digestion and ozonation for the treatment of high strength distillery wastewater (i.e., cherry stillage) is reported. Experiments were conducted in laboratory batch systems operating in draw and fill mode. For the biological step, activated sludge from a municipal wastewater treatment facility was used as inoculum, showing a high degree of activity to distillery wastewater. Thus, BOD and COD overall conversions of 95% and 82% were achieved, respectively. However, polyphenol content and absorbance at 254 nm (A(254)) could not be reduced more than 35% and 15%, respectively, by means of single biological oxidation. By considering COD as substrate, the aerobic digestion process followed a Contois' model kinetics, from which the maximum specific growth rate of microorganisms (mu(max)) and the inhibition factor, beta, were then evaluated at different conditions of temperature and pH. In the combined process, the effect of a post-ozonation stage was studied. The main goals achieved by the ozonation step were the removal of polyphenols and A(254). Therefore, ozonation was shown to be an appropriate technology to aid aerobic biological oxidation in the treatment of cherry stillage.

pH sequential ozonation of domestic and wine-distillery wastewaters.

Domestic and wine-distillery wastewaters were treated by semi-batch and continuous pH sequential ozonations. The process involves a succession of acidic and alkaline wastewater pH conditions. The alkaline periods allow oxidation of organic matter by hydroxyl radical and produce carbonates that eventually would inhibit the oxidation. On the other hand, the acidic periods favour the development of direct ozone reactions and strip off carbonates as carbon dioxide from the wastewater. Experimental results of pH sequential ozonation showed degradation and removal rates of wastewater pollutants higher than those achieved at constant either acidic or basic pH. The most significant improvement of ozone efficiency and pollutants removal were obtained by controlling the number of cycles, pH and time of acidic and alkaline phases. Also, ozonated wastewaters showed high biodegradability as deduced from their BOD/COD ratios. The feasibility of treating domestic and wine-distillery wastewater by an integrated activated sludge (ASP)-pH sequential ozonation system was evaluated. Integrated ASP-ozonation at constant pH processes were also carried out for comparative purposes. In these combined experiments, pH sequential ozonation showed advantages compared to ozonation at constant pH in reducing global parameters such as COD, TOC and TKN, but ozonation at constant pH led to higher removal of polyphenols and UV254 absorbing compounds.

Estimation of biological kinetic parameters from a continuous integrated ozonation-activated sludge system treating domestic wastewater.

The feasibility of treating municipal wastewater by a combined ozone-activated sludge continuous flow system was studied. Lab-scale experiments of both single activated sludge and combined ozone-activated sludge processes were carried out to determine the kinetic coefficients of the biological stage. The results obtained indicated a clear improvement in the kinetic parameters of the aerobic oxidation when a pre-ozonation stage was applied. Particularly, COD removal and nitrification rates were highly increased. The biokinetic parameters were also used to simulate and optimize the continuous reaction system. From the model prediction it was concluded that the integrated process (i.e., ozone-ASP) may significantly increase the waste reduction capacity. The results presented here provide a useful basis for further scaling up and efficient operation of ozone-ASP units in wastewater treatment processes.

Kinetics of simazine advanced oxidation in water.

Comparison of the effects and kinetics of UV photolysis and four advanced oxidation systems (ozone, ozone/hydrogen peroxide, ozone/UV radiation and UV radiation/hydrogen peroxide) for the removal of simazine from water has been investigated. At the conditions applied, the order of reactivity was ozone < ozone/hydrogen peroxide < UV radiation < ozone/UV radiation and UV radiation/hydrogen peroxide. Rate constants of the reactions between ozone and simazine and hydroxyl radical and simazine were found to be 8.7 M-1s-1 and 2.1 x 10(9) M-1s-1, respectively. Also, a quantum yield of 0.06 mol.photon-1 was found for simazine at 254 nm UV radiation. The high value of the quantum yield corroborated the importance of the direct photolysis process. Percentage contributions of direct reaction with ozone, reaction with hydroxyl radicals and direct photolysis were also quantified.

Wine distillery wastewater degradation. 1. Oxidative treatment using ozone and its effect on the wastewater biodegradability.

Laboratory-scale experiments were conducted to investigate the impact of ozonation on the degradability of wine distillery wastewaters, usually called vinasses, with the goal of developing combined chemical-biological methods for their treatment. Chemical oxygen demand (COD), biological oxygen demand (BOD), total organic carbon (TOC), and ultraviolet absorbance at 254 nm (UV(254)) were taken as reference parameters to follow the pollution level. The vinasses were treated both directly and after being mixed with domestic sewage. Ozonation of pure vinasses required high ozone doses to achieve a significant efficiency for removing the organic matter. Mixing vinasses with domestic sewage allowed higher degradation rates with ozone. Ozone was also demonstrated to be an appropriate oxidizing agent to improve vinasses's biodegradability and organic matter removal. A mathematical model of the ozonation kinetics based on the film theory concept is also presented.

Wine distillery wastewater degradation. 2. Improvement of aerobic biodegradation by means of an integrated chemical (Ozone)-biological treatment.

Biological degradation of vinasses, generated during alcohol production from wines and pressed grapes, has been studied in four digesters operating in fill and draw mode. Digesters 1 and 2 were fed with nonozonated and ozonated mixtures of vinasses and domestic sewage (1:10 by volume), respectively. Digesters 3 and 4 operated with pure vinasses at acid and neutral pH values, respectively. The effects of pH, temperature, and ozone dose conditions were studied. Preozonation removed inhibitory compounds and improved the growth of nitrifiers. Ozone dose is the key variable to treat a vinasse-domestic sewage effluent effectively with a combined chemical-biological system. Contois's kinetic model has been applied to experimental results, and kinetic parameters related to the maximum specific growth rate of microorganisms, mu(max), and inhibitory effects, alpha, were calculated and compared for nonozonated and ozonated wastewaters.

Cervical implantation metastasis by endometrial adenocarcinoma.

A distinct type of cervical involvement by endometrial cancer is reported and termed cervical implantation metastasis. It is believed to result from implantation of endometrial cancer on the denuded endocervix after fractional dilatation and curettage (D & C). The histologic criteria for diagnosis are: (1) the cervical implantation metastasis must be imbedded in the endocervical epithelium or superficial stroma surrounded by an implantation site of inflammatory cells and granulation tissue (free-floating cancer cells above the cervical mucosa are not acceptable as implantation tissue), (2) the histologic findings of the cervical implantation metastasis must be similar to those of the endometrial adenocarcinoma in the uterine corpus, (3) the cervical implantation metastasis must be separate from the primary tumor with no evidence of direct extension, and (4) the cervical implantation metastasis should be surrounded by nonneoplastic endocervical glands with no transition between the two. Of the 176 patients who underwent fractional D & C before hysterectomy, nine (5%) were found to have cervical implantation metastasis. No patients had cervical implantation metastasis who did not undergo fractional D & C before hysterectomy. When stratified according to stage, grade, and myometrial invasion, there was no statistically significant difference in the recurrence rate between patients with or without cervical implantation metastasis. It appears that cervical implantation metastasis does not alter prognosis or require specific treatment.

Prognostic significance of the extent of cervical involvement by endometrial cancer.

The prognostic significance of the extent of cervical involvement by endometrial cancer is impossible to determine from the literature because previous reports have included fractional dilatation and curettage for staging, preoperative radiotherapy, and surgical stage III and IV disease. Therefore, we reviewed and restaged according to the new FIGO system all patients with endometrial cancer from January 1981 to December 1989. Of 180 patients undergoing hysterectomy for endometrial cancer, 20 had surgical stage II disease. No patient received preoperative radiotherapy. None of 12 patients (0%) with stage IIA disease developed recurrence, while 5 of 8 (63%) with stage IIB disease recurred (P less than 0.01). All 5 recurrences were in extrapelvic sites. Endocervical stroma invasion appears to import a statistically significant worse prognosis than endometrial glandular involvement.