Life cycle assessment of solar photo-Fenton and solar photoelectro-Fenton processes used for the degradation of aqueous α-methylphenylglycine.

A comparative Life Cycle Assessment (LCA) of solar photo-Fenton and solar photoelectro-Fenton, two solar-driven advanced oxidation processes (AOPs) devoted to the removal of non-biodegradable pollutants in water, is performed. The study is based on the removal, at laboratory scale, of the amino acid α-methylphenylglycine, a good example of soluble and non-biodegradable target pollutant. The system under study includes chemicals, electricity, transport of all raw materials to the plant site, and the generation of emissions, but it does not take into account the impact of the infrastructure needed to build a hypothetical solar plant. Nine environmental impact categories are included in the LCA: global warming potential, ozone depletion potential, aquatic eutrophication potential, acidification potential, human toxicity potential, photochemical ozone formation potential, fresh water aquatic ecotoxicity potential, marine aquatic ecotoxicity potential, and terrestrial ecotoxicity potential and abiotic resource depletion potential. Although previous experimental results show that both AOPs are able to efficiently degrade the pollutant, the LCA indicates that solar-driven photo-Fenton is the most environmentally friendly alternative, mainly because the use of electricity in solar photoelectro-Fenton experiments involves high environmental impacts.

Zirconium-doped and silicon-doped TiO2 photocatalysts synthesis from ionic-liquid-like precursors.

Nanocrystalline titania powders doped with either zirconium or silicon were synthesized at low temperature via destabilization of ionic-liquid-like precursors. Titania materials prepared at low temperature (85 degrees C) consisted of anatase nanocrystals of about 25 nm, according to powder X-ray diffraction and transmission electron microscopy. Dopant incorporation was evaluated using inductively coupled plasma-optical emission spectrometry, and it was found that dopant/titanium ratios in the powder (0.011 for Zr and 0.026 for Si) were lower than those in the precursor (0.11 for both). Low-temperature nitrogen adsorption-desorption isotherms displayed the characteristic hysteresis loop of mesoporous materials. Specific surface areas reached values of 130 and 155 m(2) g(-1) for Zr-doped and Si-doped TiO(2), respectively. The photocatalytic activity of the synthesized nanopowders was tested using methyl orange and 4-chlorophenol as target pollutants.

Predicted environmental concentrations of cocaine and benzoylecgonine in a model environmental system.

A Mackay-type level II fugacity model has been used to predict the behaviour and final concentrations of cocaine (COC) and its main metabolite benzoylecgonine (BE) in a regional environmental system defined according to the European guidelines on Risk Assessment. The model takes into account the initial COC intake, partial degradation of the parent compound to BE, treatment of wastewater and environmental fate of these substances. Predicted environmental concentrations (PECs) lie in the ngL(-1) level, with the exception of the air compartment, where the concentrations are negligible. PECs in the water phase are in accordance with measured experimental concentrations in different European rivers. This case study shows that a simple level II fugacity model is suitable enough for modelling the environmental fate of high water soluble and low volatile organic compounds such as pharmaceuticals and personal care products.

Coupled solar photo-Fenton and biological treatment for the degradation of diuron and linuron herbicides at pilot scale.

A coupled solar photo-Fenton (chemical) and biological treatment has been used to remove biorecalcitrant diuron (42 mg l(-1)) and linuron (75 mg l(-1)) herbicides from water at pilot plant scale. The chemical process has been carried out in a 82 l solar pilot plant made up by four compound parabolic collector units, and it was followed by a biological treatment performed in a 40 l sequencing batch reactor. Two Fe(II) doses (2 and 5 mg l(-1)) and sequential additions of H2O2 (20 mg l(-1)) have been used to chemically degrade the initially polluted effluent. Next, biodegradability at different oxidation states has been assessed by means of BOD/COD ratio. A reagent dose of Fe=5 mg l(-1) and H2O2=100 mg l(-1) has been required to obtain a biodegradable effluent after 100 min of irradiation time. Finally, the organic content of the photo-treated solution has been completely assimilated by a biomass consortium in the sequencing batch reactor using a total suspended solids concentration of 0.2 g l(-1) and a hydraulic retention time of 24h. Comparison between the data obtained at pilot plant scale (specially the one corresponding to the chemical step) and previously published data from a similar system performing at laboratory scale, has been carried out.

The testing of several biological and chemical coupled treatments for Cibacron Red FN-R azo dye removal.

Several biological and chemical coupled treatments for Cibacron Red FN-R reactive azo dye degradation have been evaluated. Initially, a two-stage anaerobic-aerobic biotreatment has been assessed for different dye concentrations (250, 1250 and 3135 mg l(-1)). 92-97% decolourisation was attained during the anaerobic digestion operating in batch mode. However, no dissolved organic carbon (DOC) removal neither biogas production was observed during the process, indicating that no methanogenesis occurred. Additionally, according to Biotox and Zahn-Wellens assays, the anaerobically generated colourless solutions (presumably containing the resulting aromatic amines from azo bond cleavage) were found to be more toxic than the initial dye as well as aerobically non-biodegradable, thus impeding the anaerobic-aerobic biological treatment. In a second part, the use of an advanced oxidation process (AOP) like photo-Fenton or ozonation as a chemical post-treatments of the anaerobic process has been considered for the complete dye by-products mineralisation. The best results were obtained by means of ozonation at pH 10.5, achieving a global 83% mineralisation and giving place to a final harmless effluent. On the contrary, the tested photo-Fenton conditions were not efficient enough to complete oxidation.

Hexafluorotitanate salts containing organic cations: use as a reaction medium and precursor to the synthesis of titanium dioxide.

The straightforward modification of commercial hexafluorotitanic acid with organic derivatives containing a tetraalkylammonium cation produced stable precursor solutions with only a small fraction of water, which were then used as a reaction medium for the synthesis of nanocrystalline TiO(2).

Combined photo-Fenton and biological treatment for Diuron and Linuron removal from water containing humic acid.

A combined chemical (photo-Fenton) and biological treatment has been proposed for Diuron and Linuron degradation in water containing natural dissolved organic matter (DOM). Humic acid (HA) was used to simulate the DOM. During the photo-Fenton process ([Fe(II)]=15.9 mg L(-1), [H2O2]=202 mg L(-1), 60 min of UVA irradiation time), the chemical oxygen demand (COD), total organic carbon (TOC), toxicity (EC50(15)) and biodegradability (BOD5/COD) of the generated intermediates were assessed. A reduction of photo-Fenton efficiency was observed when HA was present in solution. This effect has been explained as the result of a UVA light screening as well as a OH* radical quenching process by the HA. After the photo-Fenton process, the initial toxic and non-biodegradable herbicides were transformed into intermediates suitable for a subsequent aerobic biological treatment that was performed in a sequencing batch reactor (SBR). Complete elimination of the intermediates in presence of HA was reached at the end of the chemical-biological coupled system. Biosorption of HA onto the aerobic biomass was characterized. The results indicate that the Freundlich model adequately describes the adsorption of HA, a phenomena that follows a pseudo second-order adsorption kinetic model.

Life cycle assessment of a coupled solar photocatalytic-biological process for wastewater treatment.

A comparative life cycle assessment (LCA) of two solar-driven advanced oxidation processes, namely heterogeneous semiconductor photocatalysis and homogeneous photo-Fenton, both coupled to biological treatment, is carried out in order to identify the environmentally preferable alternative to treat industrial wastewaters containing non-biodegradable priority hazardous substances. The study is based on solar pilot plant tests using alpha-methyl-phenylglycine as a target substance. The LCA study is based on the experimental results obtained, along with data from an industrial-scale plant. The system under study includes production of the plant infrastructure, chemicals, electricity, transport of all these materials to the plant site, management of the spent catalyst by transport and landfilling, as well as treatment of the biodegradable effluent obtained in a conventional municipal wastewater treatment plant, and excess sludge treatment by incineration. Nine environmental impact categories are included in the LCA: global warming, ozone depletion, human toxicity, freshwater aquatic toxicity, photochemical ozone formation, acidification, eutrophication, energy consumption, and land use. The experimental results obtained in the pilot plant show that solar photo-Fenton is able to obtain a biodegradable effluent much faster than solar heterogeneous photocatalysis, implying that the latter would require a much larger solar collector area in an industrial application. The results of the LCA show that, an industrial wastewater treatment plant based on heterogeneous photocatalysis involves a higher environmental impact than the photo-Fenton alternative, which displays impact scores 80-90% lower in most impact categories assessed. These results are mainly due to the larger size of the solar collector field needed by the plant.

Partial degradation of five pesticides and an industrial pollutant by ozonation in a pilot-plant scale reactor.

Aqueous solutions of a mixture of several pesticides (alachlor, atrazine, chlorfenvinphos, diuron and isoproturon), considered PS (priority substances) by the European Commission, and an intermediate product of the pharmaceutical industry (alpha-methylphenylglycine, MPG) chosen as a model industrial pollutant, have been degraded at pilot-plant scale using ozonation. This study is part of a large research project [CADOX Project, A Coupled Advanced Oxidation-Biological Process for Recycling of Industrial Wastewater Containing Persistent Organic Contaminants, Contract No.: EVK1-CT-2002-00122, European Commission, http://www.psa.es/webeng/projects/cadox/index.html] founded by the European Union that inquires into the potential coupling between chemical and biological oxidations for the removal of toxic or non-biodegradable contaminants from water. The evolution of pollutant concentration, TOC mineralization, generation of inorganic species and consumption of O3 have been followed in order to visualize the chemical treatment effectiveness. Although complete mineralization is hard to accomplish, and large amounts of the oxidant are required to lower the organic content of the solutions, the possibility of ozonation cannot be ruled out if partial degradation is the final goal wanted. In this sense, Zahn-Wellens biodegradability tests of the ozonated MPG solutions have been performed, and the possibility of a further coupling with a secondary biological treatment for complete organic removal is envisaged.

Environmental assessment of different photo-Fenton approaches for commercial reactive dye removal.

An environmental study using life cycle assessment (LCA) has been applied to three bench-scale wastewater treatments for Cibacron Red FN-R hetero-bireactive dye removal: artificial light photo-Fenton process, solar driven photo-Fenton process and artificial light photo-Fenton process coupled to a biological treatment. The study is focused on electricity and chemicals consumption, transports and atmosphere and water emissions generated by the different processes involved. Results show that the artificial light photo-Fenton process is the worst treatment in terms of environmental impact. On the other hand, both solar driven and coupled to biological photo-Fenton processes reduce significantly the environmental damage, although none can be identified as the best in all impact categories. The major environmental impact is attributed to the H2O2 consumption and to the electrical energy consumption to run the UVA lamp. An economic analysis of the different photo-Fenton processes has also been performed and the results are discussed together with those obtained from the environmental assessment.

Assessment of photo-Fenton and biological treatment coupling for Diuron and Linuron removal from water.

The coupling of photo-Fenton (chemical) and biological treatments has been used for the removal of Diuron and Linuron herbicides from water. The chemical reaction was employed as a pre-treatment step for the conversion of the toxic and non-biodegradable herbicides into biodegradable intermediates that were subsequently removed by means of a biological sequencing batch reactor (SBR). Multivariate experimental design was used to select four photo-Fenton reagent dose combinations for the coupling experiments. Concentrations of hydrogen peroxide between 10 and 250 mg L(-1), and iron (II) concentrations between 2 and 20 mg L(-1) have been tested. 15.9 mg L(-1) of Fe(II) and 202 mg L(-1) of H(2)O(2) were needed to convert initial toxic and non-biodegradable herbicides into suitable intermediates for a subsequent biological treatment. Detrimental effects due to the excess of reactants were detected. Chemical oxygen demand (COD), average oxidation state (AOS), total organic carbon (TOC) and hydrogen peroxide concentration are the parameters used to trace the experiments course. Also, toxicity (EC(50)(15)) and biodegradability (BOD(5)/COD) tests were carried out at the end of each chemical oxidation. Complete disappearance of the herbicides from water was observed after the chemical treatment, while 3,4-dichloroaniline and 3,4-dichlorophenyl isocyanate were identified as the main by-products of the degradation process. Complete TOC removal was achieved after biological treatment in a SBR using a hydraulic retention time (HRT) of 2 days.

Environmental assessment of different advanced oxidation processes applied to a bleaching Kraft mill effluent.

Different advanced oxidation processes (AOPs) have been applied to remove the organic carbon content of a paper mill effluent originating from the Kraft pulp bleaching process. The considered AOPs were: TiO(2)-mediated heterogeneous photocatalysis, TiO(2)-mediated heterogeneous photocatalysis assisted with H(2)O(2), TiO(2)-mediated heterogeneous photocatalysis coupled with Fenton, photo-Fenton, ozonation and ozonation with UV-A light irradiation. The application of the selected AOPs all resulted in a considerable decrease in dissolved organic carbon (DOC) content with variable treatment efficiencies depending upon the nature/type of the applied AOP. A Life Cycle Assessment (LCA) study was used as a tool to compare the different AOPs in terms of their environmental impact. Heterogeneous photocatalysis coupled with the Fenton's reagent proved to have the lowest environmental impact accompanied with a moderate-to-high DOC removal rate. On the other hand, heterogeneous photocatalysis appeared to be the worst AOP both in terms of DOC abatement rate and environmental impact. For the studied AOPs, LCA has indicated that the environmental impact was attributable to the high electrical energy (power) consumption necessary to run a UV-A lamp or to produce ozone.

Degradation of Procion Red H-E7B reactive dye by coupling a photo-Fenton system with a sequencing batch reactor.

A bench-scale study combining photo-Fenton reaction with an aerobic sequencing batch reactor (SBR) to degrade a commercial homo-bireactive dye (Procion Red H-E7B, 250mgl(-1)) was investigated. The photo-Fenton process was applied as a pre-treatment, avoiding complete mineralisation, just to obtain a bio-compatible water able to be treated by means of the SBR in a second step. In this sense, different Fenton reagent concentrations were assessed by following dye solution biodegradability enhancement (BOD(5)/COD), as well as the toxicity (EC(50)), DOC, colour (Abs(543.5)) and H(2)O(2) evolution with photo-Fenton irradiation time. Obtained pre-treated solutions were biologically oxidized in a SBR containing non-acclimated activated sludge. Different hydraulic retention time (HRT) in the bioreactor were tested to attain the maximum organic load removal efficiency. Best results were obtained with 60min of 10mgl(-1) Fe(II) and 125mgl(-1) H(2)O(2) photo-Fenton pre-treatment and 1 day HRT in SBR.

Aluminium(III) adsorption: a soft and simple method to prevent TiO2 deactivation during salicylic acid photodegradation.

Deposition of poisoning species on TiO2 during salicylic acid photodegradation can be halted when Al(III) has been previously adsorbed on the catalyst surface; this widens the application of photocatalysis to more concentrated solutions.

Degradation of some biorecalcitrant pesticides by homogeneous and heterogeneous photocatalytic ozonation.

Photo-Fenton/ozone (PhFO) and TiO2-photocatalysis/ozone (PhCO) coupled systems are used as advanced oxidation processes for the degradation of the following biorecalcitrant pesticides: alachlor, atrazine, chlorfenvinfos, diuron, isoproturon and pentachlorophenol. These organic compounds are considered Priority Hazardous Substances by the Water Framework Directive of the European Commission. The degradation process of the different pesticides, that occurs through oxidation of the organic molecules by means of their reaction with generated OH radical, follows a first and zero-order kinetics, when PhFO and PhCO are applied, respectively. These two Advanced Oxidation Processes, together with the traditional ozone+UV, have been used to investigate TOC reduction of the different pesticide aqueous solutions. The best results of pesticide mineralization are obtained when PhFO is applied; with the use of this advanced oxidation process the aqueous pesticide solutions become detoxyfied except in the case of atrazine and alachlor aqueous solutions for which no detoxification is achieved at the experimental conditions used in the work, at least after 2 and 3 h of treatment, respectively.

Solar activated ozonation of phenol and malic acid.

The effect that sunlight has on the degradation rate of two model organic compounds, phenol and malic acid, by ozone is studied. The effect seems to be due to both direct light absorption (300-320 nm photons) by ozone, which produces the pollutant degradation, and light absorption by reaction intermediates. The presence of such a light notably improves the reactivity of ozone toward the organic species, leading to a faster and complete mineralization even at large initial total organic carbon values. The use of artificial sunlight (Xe lamp) is also explored. Finally, the simultaneous presence of sunlight and other ozone degradation catalyst like transition metal ions is studied, showing the beneficial effect of such a combination.

Fenton and photo-Fenton oxidation of textile effluents.

The simultaneous use of Fenton reagent and irradiation for the treatment of textile wastewaters generated during a hydrogen peroxide bleaching process is investigated. The experimental conditions tested during this study provide the simultaneous occurrence of Fenton, Fenton-like and photo-Fenton reactions. The batch experimental results are assessed in terms of total organic carbon reduction. Identification of some of the chemical constituents of the effluent was performed by means of GC-MS. Other pollution related features of the initial effluent-like COD and color were also measured. The main parameters that govern the complex reactive system, i.e., light intensity, temperature, pH, Fe(II) and H2O2 initial concentrations have been studied. Concentrations of Fe(II) between 0 and 400 ppm, and H2O2 between 0 and 10,000 ppm were used. Temperatures above 25 degrees C and up to 70 degrees C show a beneficial effect on organic load reduction. A set of experiments was conducted under different light sources with the aim to ensure the efficiency of using solar light irradiation. The combination of Fenton, Fenton-like and photon-Fenton reactions has been proved to be highly effective for the treatment of such a type of wastewaters, and several advantages for the technique application arise from the study.

How green is a chemical reaction? Application of LCA to green chemistry.

In the present work Life Cycle Assessment (LCA) is used in order to evaluate a chemical reaction from an environmental point of view. The objective is to assess the usefulness of this methodology as an environmental tool to be applied to green chemistry. As an example, two routes of obtaining maleic anhydride are compared using LCA, to ascertain which one is the most environmentally friendly. From the results obtained in this work it can be concluded that LCA seems to be a valuable tool for the environmental assessment of a chemical reaction, because it takes into account all the life cycle stages of the process and discusses the impact of the environmental burdens inventoried according to a diversity of impact categories.