Monopersulfate in water treatment: Kinetics.

The kinetics of monopersulfate based systems in the elimination of potential harmful contaminants has been assessed from a theoretical point of view. A detailed reaction mechanism sustained in the generation of radicals (mainly hydroxyl and sulfate), propagation and termination stages has been proposed. The system of first order differential equations derived has numerically been solved. The effect of main influencing parameters such as contaminant and peroxymonosulfate initial concentrations, intermediate generation, presence of organic matter, role played by anions, has been theoretically obtained. Discussion of simulated results has been accomplished by comparison with experimental data found in the literature. At the sight of the theoretical and empirical data, use of simplistic pseudo first order kinetics is discouraged. Despite considering a significant number of elemental reactions, modelling of the system reveals that a high fraction of them can be neglected due to their insignificant role played in the mechanism. The entire mechanism has been tested when peroxymonosulfate has been activated by UV radiation, although results can be fairly extrapolated to other activation strategies. Finally, a generic model capable of accounting for the effect of a diversity of parameters is proposed. No theoretical background is behind the model, however the generic model clearly improves the results obtained by simple first order kinetics.

Peroxymonosulfate/solar radiation process for the removal of aqueous microcontaminants. Kinetic modeling, influence of variables and matrix constituents.

New technologies to address the presence of pharmaceutical and personal care products (PPCPs) in wastewater are needed, especially in those cases in which water will be reused. In this work, the activation of peroxymonosulfate (PMS) with simulated solar radiation has been applied to the oxidation of a mixture of six PPCPs, i.e. caffeine, primidone, N,N-diethyl-3-methylbenzamide (DEET), methylparaben, clofibric acid and ibuprofen. The sole application of solar radiation, i.e. solar photolysis, only led to the oxidation of clofibric acid (complete degradation in 90 min). The combination of PMS and solar radiation resulted in the degradation of all target micropollutants. The complete degradation of this mixture at initial 100 ppb was achieved with 0.5 mM of initial PMS after 90 min. A kinetic study that acceptably simulates the experimental data under different conditions has been proposed. The effects of initial PPCP concentration (1 mg L-1-100 µg L-1), PMS dose (0.1-5 mM), and pH (3-9) were tested and kinetically simulated. Finally, the PPCPs removal study was carried out in two real water matrices (river and a secondary effluent of an urban wastewater treatment plant). A higher dose of PMS, ten times higher, was required to achieve complete degradation of the micropollutants if compared to ultrapure water.

Simulated solar photo-assisted decomposition of peroxymonosulfate. Radiation filtering and operational variables influence on the oxidation of aqueous bezafibrate.

This work investigates the potential of the combination of peroxymonosulfate (PMS) and simulated solar radiation (λ > 300 nm) to remove bezafibrate from aqueous solution. Different solar light filters indicate a higher removal efficiency as the wavelength range used moves to the more energetic region of the solar spectrum. The system PMS/Daylight (300-800 nm) eliminates bezafibrate (1 mg L-1) in less than 30 min under the best conditions used in this study (CPMS = 4·10-4 M) with no pH control (acidic pH). The efficiency of the process significantly improves under alkaline conditions (pH = 10), likely due to a higher PMS photolysis rate. Experiments conducted at different initial concentration of PMS and bezafibrate suggest first order regarding PMS and different from 1 in the case of bezafibrate. Intermediates generated at the beginning of the process have been tentatively identified to propose a hypothetical reaction pathway and to estimate their toxicity.

Sunlight driven photolytic ozonation as an advanced oxidation process in the oxidation of bezafibrate, cotinine and iopamidol.

This study investigates the efficacy of the system O3/sunlight radiation compared to dark ozonation when treating pharmaceuticals compounds of different reactivity, namely bezafibrate, cotinine, and iopamidol. Results show the beneficial effects of simulated sunlight radiation (300-800 nm) when treating ozone recalcitrant compounds such as cotinine and iopamidol. The system O3/sunlight radiation increased mineralization extent in all cases if compared to dark ozonation. Transformation products identified in individual runs suggest that amine oxidation and further alkyl chain attack is the main route of bezafibrate ozonation. Hydroxylation seems to be the preferential path in cotinine abatement while H abstraction from alcoholic moieties is suggested in the case of iopamidol. Toxicity of intermediates was approximately evaluated by QSAR methodologies and experimentally through Daphnia Magna survival after 24 h. As a rule of thumb, initial intermediates generated are even more toxic than parent compounds, however, after 120 min of treatment, toxicity significantly decreased. Amongst the most toxic compounds generated: 4-Chlorobenzoyltyramine, and 4-Chloro-N-[2-(3,4-dihydroxy-phenyl)-ethyl]-benzamide (from bezafibrate), and N-(2-Hydroxy-1-hydroxymethyl-ethyl)-N'-(1-hydroxymethyl-2-oxo-ethyl)-5-(2-hydroxy-propionylamino)-2,4,6-triiodo-isophthalamide, N,N'-Bis-(1-hydroxymethyl-2-oxo-ethyl)-5-(2-hydroxy-propionylamino)-2,4,6-triiodo-isophthalamide, and N-(1-Hydroxymethyl-2-oxo-ethyl)-5-(2-hydroxy-propionylamino)-2,4,6-triiodo-isophthalamide (from iopamidol) were identified.

Peroxymonosulfate promoted wet air oxidation of a real wastewater from a biodiesel production plant.

Wastewater from a real biodiesel plant located in the province of Badajoz (Spain) has been treated by means of the Wet air oxidation (WAO) process. The effluent was slightly acidic (pH = 5.77) with a high content of chemical oxygen demand (COD) (43.1 g L-1) mainly of organic nature (CTOC = 10.5 g L-1). The low biodegradability of this effluent (relation biological-chemical oxygen demand BOD/COD = 8.6 × 10-3), suggests the suitability to be treated by WAO oxidation. The main WAO operational variables (oxygen pressure, temperature and pH), the use of homogeneous catalysis (Cu2+), or the addition of oxidant promoters (H2O2 or peroxymonosulfate (PMS)) were explored. From the results obtained, oxygen pressure exerted a positive effect while temperature was a crucial variable in the oxidation of the most recalcitrant organics. Although alkaline pH led to an improved behavior in terms of COD and TOC removals, the lack of aromatic compounds elimination (absorbance at 254 nm) suggests the preference to oxidize non-aromatic compounds. Addition of radical promoters resulted in a positive effect. Peroxymonopersufate was more efficient than H2O2 in the promoted experimental series. Under the optimum oxidation conditions used in this study, removals of 55% in COD, 45% in TOC and 86% in aromatic compounds were experienced.

Simulated solar driven photolytic ozonation for the oxidation of aqueous recalcitrant-to-ozone tritosulfuron. Transformation products and toxicity.

This work reports the combination of ozone and solar radiation as an advanced oxidation process to remove the herbicide tritosufuron (TSF) in water. Firstly, the recalcitrance of TSF has been assessed, obtaining an ozonation second order rate constant of 5-154 M-1 min-1 in the range of pH from 5 to 8; while the rate constant with HO was found to be (1.8-3.1)·109 M-1 s-1. Secondly, the simultaneous application of simulated solar radiation in between 300 and 800 nm and ozone resulted positive in the oxidation rate of TSF. Mineralization extent was also higher. Less effective oxidation was achieved after limiting the radiation to the range 360-800 nm or 390-800 nm; also completely inappropriate for mineralization. Thirdly, the detected transformation products (TPs) demonstrated the vulnerability of TSF molecule to be attacked by HO in the sulfonylurea bridge. The combination of ozone and radiation of 300-800 nm led to the most effective removal of the TPs. Finally, after the photolytic ozonation treatment toxicity was also evaluated in terms of phytotoxicity towards the germination and root elongation of Lactuca Sativa seeds, and toxicity by immobilization tests of Daphnia Magna.

Monopersulfate photocatalysis under 365 nm radiation. Direct oxidation and monopersulfate promoted photocatalysis of the herbicide tembotrione.

Oxone(®) (potassium monopersulfate, MPS) has been used to oxidize the herbicide tembotrione in aqueous solution. Tembotrione elimination kinetics by MPS direct oxidation has been studied. The influence of the main operating variables affecting the process (MPS concentration, temperature and pH) has been evaluated. The process follows 2/3 and first orders in MPS and tembotrione concentrations, respectively. Optimal pH is located around circumneutral conditions. MPS decomposition in the presence of 365 nm UVA radiation and titanium dioxide has also been studied. A kinetic mechanism that simulates MPS decomposition has been proposed, showing the positive effect of titania load and MPS concentration. The system MPS/UVA/TiO2 significantly improves tembotrione and mineralization rate abatement if compared to runs conducted in the absence of MPS. Tembotrione total abatement was achieved in 20 min when 0.05 g L(-1) of titania and 10(-4) M of Oxone(®) were used. TOC conversion was roughly 70% in 90 min under similar operating conditions. An experimental design (Plackett-Burman) has been considered to study the influence of the main variables affecting tembotrione photocatalytic oxidation promoted by MPS.

Removal of emergent contaminants: integration of ozone and photocatalysis.

A mixture of nine pharmaceuticals has been treated by means of the systems: UV-B(313 nm), O(3), UV-B(313 nm) + TiO(2), O(3) + UV-B(313 nm), and O(3) + UV-B(313 nm)+TiO(2). Simple photolytic or ozonation processes lead to a deficient total organic carbon (TOC) elimination after 120 min of exposure (25 and 30% conversions, respectively). Addition of a photocatalyst such as titanium dioxide significantly enhanced the mineralization degree, a 60% TOC conversion was obtained. A TiO(2) load optimum around 0.25 g L(-1) was observed. No loss in photoactivity was experienced after 2 reuses. Due to ozone photodegradation, the combination of ozone and radiation increased the generation of hydroxyl radicals. As a consequence, TOC removal was increased to a value in the proximity of 85%. The most complex system, O(3) + UV-B(313 nm) + TiO(2), achieved the highest TOC abatement (95%). Use of ozone in photocatalytic processes involves an increase in hydroxyl radical generation.

Intracranial hypertension in two cases of craniometaphyseal dysplasia: differing surgical options.

Craniometaphyseal dysplasia (CMD) is a very rare bone disorder characterized by abnormally developed metaphyses in long bones and sclerosis of the craniofacial bones. In this paper, the authors report 2 cases of children diagnosed with CMD and chronic intracranial hypertension with deletion in exon 9 of the human ANK gene (ANKH). After intracranial monitoring, a different treatment was chosen for each patient. One of the patients was treated using CSF shunting because ventriculomegaly in the absence of a Chiari malformation was also observed on cerebral MR imaging. The other patient underwent cranial expansion and decompressive craniotomy of the posterior fossa, because ventriculomegaly was excluded after cerebral MR imaging and cervical MR imaging showed a Chiari malformation Type I. The origin of intracranial hypertension in CMD is multifactorial. Previous intracranial pressure monitoring and a thorough understanding of neuroimaging studies are essential to achieve an accurate diagnosis and effective treatment.

Promoted wet air oxidation of polynuclear aromatic hydrocarbons.

The treatment of an aqueous solution of four polycyclic aromatic hydrocarbons, namely acenaphthene, phenanthrene, anthracene and fluoranthene, under moderate conditions of temperature and pressure has been conducted in the presence and absence of free radical promoters (hydrogen peroxide or potassium monopersulfate). With no addition of promoters, the process achieves PAH conversion values in the range 80-100% at 190 degrees C and 50 bars of air pressure (80 min of reaction). Similar results are obtained in the presence of hydrogen peroxide, however, in this case, the time required is just 60 min with a sharp decrease in PAH concentration in the first 10-20 min. Additionally, temperature can be lowered to values in the range 100-150 degrees C. If potassium monopersulfate is used instead of hydrogen peroxide, an analogous behaviour is experienced, in the latter case, temperatures above 120 degrees C lead to an inhibition of anthracene oxidation, likely due to ineffective decomposition of the monopersulfate molecule.

Photocatalytic ozonation of winery wastewaters.

The combination of UV-A/vis radiation and ozone, in the presence of titanium dioxide, has been investigated as a potential destructive technology for the treatment of winery wastewaters. The contribution of the adsorption stage, single ozonation, photolytic ozonation, and photocatalysis has previously been assessed. Adsorption onto the TiO 2 surface accounts for a 15-20% removal of the initial chemical oxygen demand (COD). The rest of the subsystems attain COD conversion values in the range of 37-43%. The photocatalytic ozonation of the effluent, under the operating conditions investigated, increases the COD depletion to a value close to 80%. The working pH was studied in the range of 3-11, the optimum value being located in the acidic region (pH 3). A saturation-like behavior is experienced when the amount of TiO 2 used is varied in the interval of 0-3 g L(-1). Contrary to the use of ozone alone, the system UV-A/vis/O3/TiO2 leads to the total mineralization of the COD removed. A proposed pseudoempirical model suggested the existence of a synergistic effect when radiation, ozone, and titanium dioxide are combined.

Photocatalytic promoted oxidation of phenolic mixtures: an insight into the operating and mechanistic aspects.

The photocatalytic oxidation of a phenolic mixture (gallic acid, tyrosol and syringic acid) has been carried out in the presence of titanium dioxide and a selected inorganic peroxide, namely persulphate, monopersulphate or hydrogen peroxide. The results obtained in UVA irradiated solutions reveal that hydrogen peroxide is the most effective option. The influence of some relevant operating parameters (i.e. initial concentration of phenols, hydrogen peroxide or titanium dioxide) has been investigated. In all cases a saturation-like behaviour has been observed. Thus, an increase in oxidation efficiency is observed when raising, up to a certain value, the initial amounts of reagents/catalyst added to the reactor. Nevertheless, a further increase of any of the previous parameters does not lead to the expected enhancement of the process. From the concave shape of the parent compounds' depletion profiles, it is suggested that the system proceeds through an autocatalytic route, likely involving the action of organic radicals. A pseudoempirical model has been used to acceptably model the experimental data obtained.

Polycyclic aromatic hydrocarbons sorbed on soils: a short review of chemical oxidation based treatments.

A brief review is completed on the chemical oxidation of PAHs contaminated soils. Previously, the adsorption and extraction processes are also documented and discussed. The tree main technologies reported in the specialised literature include the use of ozone, hydrogen peroxide (with or without ferrous iron addition) and high temperature pressurized water (both in sub- and super-critical conditions) in the presence of an added oxidant like hydrogen peroxide, oxygen, persulfate, etc. Each process is detailed by the influence of the main operating variables reported in the literature (i.e. presence of organic matter, soil type, reagents dosage, etc.), the kinetics and the description of integrated treatments (i.e. chemical oxidation + biodegradation).

Phenol and substituted phenols AOPs remediation.

The oxidation of phenol and two substituted species (4-nitrophenol and 4-chlorophenol) has been carried out by means of the O3, UV-vis, O3+UV-vis, TiO2+UV-vis, O(3)+UV-vis+TiO2 and O3+TiO2 systems. From UV-vis experiments, the quantum yield of these organics has been calculated (0.018, 0.005 and 0.017 mol per Einstein for phenol, 4-nitrophenol and 4-chlorophenol, respectively). Broadly speaking, the addition of titania powder results in a slight inhibition of the parent compound degradation rate, although a positive effect is experienced when measuring the chemical oxygen demand (COD) and total organic carbon (TOC) removals. Amongst the technologies investigated, those combining ozone and radiation show the best efficiency in terms of phenols elimination and also COD and TOC decay rates. A simple economy analysis of the processes illustrates how the combinations O3+UV-vis and O3+UV-vis+TiO2 are the most attractive technologies, although some additional considerations have to be taken into account.

Aqueous ozone decomposition onto a Co2O3-alumina supported catalyst.

The aqueous ozone decomposition in the presence of a Co2O3-Alumina catalyst was investigated. Activity and estability assays were conducted by reusing the same catalyst in consecutive runs. The catalyst was shown to significantly increase the ozone abatement rate without loss in activity after five consecutive experiments. The process can be acceptably simulated by a double homogeneous-heterogeneous decomposition mechanism. An increase in the working temperature resulted in an opposite effect by increasing the extension of the homogeneous decomposition and lowering the extension of the heterogeneous decomposition. Similarly, different trends were observed by adding two distinct free radical scavengers (terc-butyl alcohol and carbonates).

Stabilized leachates: sequential coagulation-flocculation + chemical oxidation process.

The combined sedimentation-chemical oxidation treatment of medium-stabilized landfill leachates has been investigated. The sequence of stages implemented was: (a) coagulation-flocculation by pH decrease (pH 2) to acidic conditions (COD removal approximately 25% related to COD0 approximately 7500 ppm); (b) coagulation-flocculation by Fe(III) addition (0.01 M) at pH 3.5 (COD removal approximately 40% related to COD of supernatant after step (a); (c) Fenton (Fe(III) = 0.01 M; H2O2 = 1.0 M) oxidation (COD removal approximately 80% related to COD of supernatant after step (a); and (d) coagulation-flocculation of Fenton's effluent at pH 3.5 (COD removal approximately 90% related to COD of supernatant after step (a). The use of Kynch theory allows for the design of clarifiers based on the amount of solids fed. For a general example of 1000 m3 day(-1) of a feeding stream, clarifier area values of 286,111 and 231 m2 were calculated for compacting indices of 3.7, 2.67 and 2.83 corresponding to the first, second and third consecutive sedimentation processes, respectively, (steps (a), (b) and (d)).

Wet peroxide degradation of atrazine.

The high temperature (150-200 degrees C), high pressure (3.0-6.0 MPa) degradation of atrazine in aqueous solution has been studied. Under these extreme conditions atrazine steadily hydrolyses in the absence of oxidising agents. Additionally, oxygen partial pressure has been shown not to affect atrazine degradation rates. In no case mineralisation of the parent compound was observed. The addition of the free radical generator hydrogen peroxide to the reaction media significantly enhanced the depletion rate of atrazine. Moreover, partial mineralisation of the organics was observed when hydrogen peroxide was used. Again, oxygen presence did not influence the efficiency of the promoted reaction. Consecutive injections of hydrogen peroxide throughout the reaction period brought the total carbon content conversion to a maximum of 65-70% after 40 min of treatment (suggesting the total conversion of atrazine to cyanuric acid). Toxicity of the effluent measured in a luminometer decreased from 93% up to 23% of inhibition percentage. The process has been simulated by means of a semi-empirical model.

Stabilized leachates: ozone-activated carbon treatment and kinetics.

Ozone has been used as a pre-oxidation step for the treatment of stabilized leachates. Given the refractory nature of this type of effluents, the conversion of some wastewater quality parameters has been moderate after 1 h of ozonation (i.e. 30% chemical oxygen demand (COD) depletion). Ozone uptake was calculated in the interval 1.3-1.5 g of ozone per gram of COD degraded. An optimum dose of ozone has been experienced in terms of biodegradability of the processed effluent (60 min of treatment, 1 x 10(-3) mol L(-1) ozone inlet feeding concentration and 50 L h(-1) gas flow-rate). pH and other typical hydroxyl radical generator systems exerted no influence on the efficiency of the process, suggesting the negligible role played by the indirect route of oxidation (generation of hydroxyl radicals). The ozonated effluent was thereafter treated in a second adsorption stage by using a commercial activated carbon. Removal levels up to 90% of COD in approximately 120 h were experienced for adsorbent dosages of 30 g L(-1). Both steps, the single ozonation and the adsorption stage have been modelled by using different pseudoempirical models.

Fenton-like oxidation of landfill leachate.

The treatment of stabilized leachates by means of Fenton's like reagent [Fe(III)-H2O2] has been studied. It has been demonstrated that the oxidation state of the catalyst does not influence the efficacy of the process in terms of chemical oxygen demand depletion profiles. The abrupt increase in temperature experienced in oxidation experiments involves a wastage of hydrogen peroxide diminishing the fraction of this reagent addressed at removing COD. If temperature is kept constant, the hydrogen peroxide uptake is 10 mg of H2O2 consumed per mg of COD abated (from 15 to 30 degrees C). Working temperatures above 30 degrees C does not lead to additional COD conversion, contrarily, the percentage of wasted H2O2 is increased. A rough economic analysis of the process indicates that this treatment can be a suitable alternative to deal with this type of effluents.