Novel approach over template molecule elimination in molecularly imprinted polymers by using heat activated persulfate.

This study proposes a new alternative for template removal from molecularly imprinted polymers by heat activated persulfate. It is known that trace amounts of template molecule remains in the polymer network after extraction by current methodologies leading to bleeding and incomplete removal of template which could compromise final determination of target analytes especially in trace analysis. A previously developed molecularly imprinted polymer specially designed for Coenzyme Q10 (CoQ10) extraction was employed as a model to test this template elimination approach. This polymer is based on methacrylic acid and ethylene glycol dimethylacrylate as monomers and Coenzyme Q0 as template. This coenzyme has the same quinone group as the CoQ10. Selectivity was analyzed comparing the recovery of CoQ10 and ubichromenol, a CoQ10 related substance. Chemical degradation using heat-activated persulfate allows the elimination of the template molecule with a high level of efficiency, being a simple and ecological methodology, yielding a polymer that exhibits comparable selectivity and imprinting effect with respect to traditional extraction methods.

Rice husk-based pyrogenic carbonaceous material efficiently promoted peroxymonosulfate activation toward the non-radical pathway for the degradation of pharmaceuticals in water.

Pristine pyrogenic carbonaceous material (BRH) obtained from rice husk and modified with FeCl3 (BRH-FeCl3) were prepared and explored as carbocatalysts for the activation of peroxymonosulfate (PMS) to degrade a model pharmaceutical (acetaminophen, ACE) in water. The BRH-FeCl3/PMS system removed the pharmaceutical faster than the BRH/PMS. This is explained because in BRH-FeCl3, compared to BRH, the modification (iron played a role as a structuring agent mainly) increased the average pore diameter and the presence of functional groups such as -COO-, -Si-O-, or oxygen vacancies, which allowed to remove the pollutant through an adsorption process and significant carbocatalytic degradation. BRH-FeCl3 was reusable during four cycles and had a higher efficiency for activating PMS than another inorganic peroxide (peroxydisulfate, PDS). The effects of BRH-FeCl3 and PMS concentrations were evaluated and optimized through an experimental design, maximizing the ACE degradation. In the optimized system, a non-radical pathway (i.e., the action of singlet oxygen, from the interaction of PMS with defects and/or -COO-/-Si-O- moieties on the BRH-FeCl3) was found. The BRH-FeCl3/PMS system generated only one primary degradation product that was more susceptible to biodegradation and less active against living organisms than ACE. Also, the BRH-FeCl3/PMS system induced partial removals of chemical oxygen demand and dissolved organic carbon. Furthermore, the carbocatalytic system eliminated ACE in a wide pH range and in simulated urine, having a low-moderate electric energy consumption, indicating the feasibility of the carbocatalytic process to treat water polluted with pharmaceuticals.

Degradation of xanthene-based dyes by photoactivated persulfate: experimental and computational studies.

Dyes are naked-eye detectable even at low concentration levels and can cause environmental damage when released into aquatic effluents; therefore, methods for removing the residual color from the aquatic media are always a current issue. In this paper, degradation of three xanthene dyes, Rhodamine B, Eosin Y, and Sodium Fluorescein, using photoactivated persulfate was evaluated at pH 3.0 and 11.0. The dyes' degradation followed a pseudo-first-order reaction. Although the solution is completely decolorized in 40 min at pH 3.0, achieving 75% mineralization requires a longer reaction time of 180 min. Furthermore, GC-MS analyses indicate that degradation products are mainly low-molecular weight acids, CO2 and H2O. Experiments carried out in dark and under UV irradiation showed substantial contribution of radical (SO4•- and HO•) and non-radical pathways to dye degradation in both pH. Additionally, to get more insights into the degradation pathways, HOMO-LUMO energy gaps of the dyes were calculated by DFT using MPW1PW91/MidiXo level of theory and, in general, the lower the bandgap, the faster the degradation. Fukui functions revealed that the preferential sites to radical attack were the xanthene or the benzoate portion depending on the pH, wherein attack to the xanthene ring provided better kinetic and mineralization results.

Hexachlorocyclohexane chemical remediation of a contaminated site in Argentina.

This work describes the complete decontamination of three parcels of a dump site located in Lomas de Zamora county, Buenos Aires province (Argentina) heavily polluted with hexachorocyclohexane (HCH), where phytoremediation, successful in the surrounding areas, was ineffective. HCH contained in contaminated soil (10 g/kg average) was oxidized with sodium persulfate activated with citric acid chelated Fe(II). This chemical remediation process required treatment in situ in each parcel of approximately 10900 tons total of soil that were mechanically removed and initially mixed with 1750 tons of sodium persulfate. The mixture was then transferred to the excavation site, and 105 tons of ferrous sulfate and 35 tons of citric acid were finally added. The process, started in January 2011 and completed in February 2016, was very effective since chemical remediation average efficiency in the three parcels was higher than 99.99%. To the best of our knowledge this work is the first demonstration that persulfate oxidation activated with citric acid chelated Fe(II) can be successfully applied for field remediation of a relatively large area.

Influence of water matrix components and peroxide sources on the transformation products and toxicity of tebuthiuron under UVC-based advanced oxidation processes.

Coupling of UV-C irradiation to different peroxides (H2O2, S2O82- and HSO5-) has great potential to degrade persistent organic compounds due to the formation of HO• or SO4•- species. However, an in-depth comparison between the performance of different UV-C/peroxide processes as a function of (i) target compound degradation, (ii) generated transformation products and (iii) lethal/sub lethal toxicity effects has not yet been performed. To this end a comparison study was carried out to evaluate the effectiveness of different UV-C/peroxide processes using the herbicide tebuthiuron (100 or 500 µg L-1) as a model pollutant. TBH degradation experiments were performed at lab-scale in real municipal wastewater treatment plant effluent and distilled water. Faster degradation occurred by increasing peroxide concentration from 735 to 2206 µmol L-1 in the municipal wastewater treatment plant effluent, mainly for S2O82-. Experiments performed in the presence of peroxide trapping agents - HO• and SO4•- (methoxibenzene) or HO• (2-propanol) - revealed that oxidation in the UV-C/S2O82- system occurs mainly through SO4•-. Lower toxicity for the MWWTP effluent was obtained after oxidative treatments using hydrogen peroxide or monopersulfate as oxidants which react mainly through HO• radicals. Two mechanistic pathways were proposed for tebuthiuron degradation: (i) hydrogen abstraction by HO• (H2O2 and HSO5-) and (ii) electron transfer by SO4•- (S2O82-). In addition, one unprecedented transformation product was identified. In conclusion, results emphasize the relevance of comparing the degradation of toxic compounds in the presence of different peroxide sources and matrices and simultaneouly evaluating responses chemical and biological endpoints.

UVA/persulfate-driven nonylphenol polyethoxylate degradation: effect of process conditions.

UV/persulfate (UV/PS) technologies have gained increased attention as efficient alternatives for removing pollutants from different classes, although processes based on the UVA-driven S2O82- (PS) activation have not yet been discussed in the literature for the removal of the nonionic surfactant nonylphenol polyethoxylate (NPEO). The present study investigated the simultaneous effect of the initial persulfate concentration ([PS]0) and specific photon emission rate (EP,0) on NPEO degradation by UVA/PS following a Doehlert experimental design. The results for [NPEO]0 = (4.65 ± 0.15) mg L-1 indicated more than 97.8% NPEO removal after 2 h, with pseudo first-order specific degradation rate (kobs) of 0.0320 min-1, for [PS]0 = 7.75 mmol L-1 and EP,0 = 0.437 µmol photons L-1 s-1. Under these conditions, NPEO half-life time was about 22 min, and the EC50-48 h (% v/v) values for Daphnia similis before and after treatment did not differ significantly. Higher values of EP,0 would influence NPEO removal for [PS]0 not higher than 8-10 mmol L-1, although lower degradation efficiencies were obtained with higher [NPEO]0 or real wastewater, except for longer reaction times. Additionally, UVA/PS showed to be efficient for tensoactivity removal, despite the negligible total organic carbon (TOC) removal achieved. Finally, UVC and UVA resulted in NPEO degradation higher than 96% and similar tensoactivity removals when UVA/PS was conducted under optimal conditions ([PS]0 = 10 mmol L-1; EP,0 = 0.324 µmol photons L-1 s-1), suggesting that UVA radiation available in solar light could be advantageously employed for NPEO removal at concentrations usually found in wastewater.

Ultrafiltration ceramic membrane as oxidant-catalyst/water contactor to promote sulfate radical AOPs: a case study on 17ß-estradiol and 17α-ethinylestradiol removal.

This work highlights the performance of an ultrafiltration ceramic membrane as photocatalyst support and oxidant-catalyst/water contactor to promote sulfate radical advanced oxidation processes (SR-AOPs). Peroxydisulfate (PDS) activation mechanisms include photolysis (UVC irradiation) and chemical electron transfer (TiO2-P25 photocatalysis). The photoreactor is composed of an outer quartz tube (the "window"-radiation entrance to the reactor) and an inner tubular ceramic ultrafiltration membrane, where the catalyst particles (TiO2-P25) are immobilized on the membrane shell-side. PDS stock solution is fed by the lumen side of the membrane, delivering the oxidant to the catalyst particles and to the annular reaction zone (ARZ), being the catalyst and PDS activated by UV light. The design facilitates controlled radial slip of PDS into the catalyst surface and to concurrent water to be treated, flowing with a helix trajectory in the ARZ. Under continuous mode operation, with an UV fluence of 45 mJ cm-2 (residence time of 4.6 s), the UVC/PDS/TiO2 system showed the best removal efficiency for two specific endocrine disrupting chemicals, 17ß-estradiol (E2) and 17α-ethinylestradiol (EE2), spiked (100 µg L-1 each) in demineralized water and urban wastewater after secondary treatment.

Dodecylpyridinium chloride removal by persulfate activation using UVA radiation or temperature: experimental design and kinetic modeling.

The degradation of dodecylpyridinium chloride (DPC) by SO4•- and HO• radicals, generated by UVA and thermal-activated persulfate (PS) was investigated. Temperatures of 30-50°C were used for the heat activation of PS. In the case of UVA/PS, the effects of [PS]0 and specific photon emission rate (EP,0) were studied through a Doehlert design coupled with statistical analysis and response surface methodology. The results showed high DPC removal (99.8%) and pseudo-first-order degradation rate (kobs = 0.0971 min-1) for [DPC]0 = 4.60 ± 0.11 mg L-1, [PS]0 = 7.75 mmol L-1, and EP,0 = 0.437 µmol photons L-1 s-1, with a major role of SO4•- radicals in comparison with HO•. The specific DPC degradation rate found under these conditions was higher than that observed for thermal activation at 50°C and [PS]0 = 5.5 mmol L-1 (kobs = 0.0712 min-1) over the same time, although complete DPC removal was also achieved in the latter. The positive effect of EP,0 on DPC degradation by the UVA/PS process depends on PS concentrations, with kobs values increasing linearly with [PS]0 in the range 7.75-10 mmol L-1, whereas lower EP,0 values can be compensated by increasing [PS]0 up to about 10 mmol L-1, without significant scavenging. The second-order rate constants of DPC with HO• and SO4•-, estimated by comprehensive kinetic modeling, were 8.26 × 109 and 4.44 × 109 L mol-1 s-1, respectively. Furthermore, higher [DPC]0 would negatively affect the DPC degradation rate by the UVA/PS process, while 62% DPC removal was obtained in WWTP water, which can be considered good given the complexity of the real matrix. Finally, our results shed light on the possibility of using available UVA radiation (4.5%) in solar irradiance on the Earth's surface, making this treatment process more sustainable and cost-effective.

A vessel-inside-vessel microwave-assisted digestion method based on SO3 generation in situ for the mineral determination of fatty samples.

Vessel-inside-vessel microwave-assisted acid digestion was developed for the analysis of samples with high-unsaturated fat content. For the first time, thermal decomposition of (NH4)2S2O8 solutions was evidenced for SO3 generation in situ and gas-phase modification in pressurized digestion flasks. NMR analysis demonstrated the oxidative effect of SO3 on olefin double bonds despite incomplete mineralization of oil samples. In this context, (NH4)2S2O8 decomposition was used in association with HNO3 solutions for sample digestion and mineral determination in edible oils (safflower, coconut, flaxseed, and chia). For all oils, dissolved organic carbon (DOC) contents lower than 5% m m-1 were obtained under optimum conditions: 210 °C with an irradiation time of 40 min, 7.0 mol L-1 HNO3 and 2.0 mol L-1 (NH4)2S2O8 in 0.9 mol L-1 H2SO4. Thus, a DOC reduction of about 70% was reached compared to digestions using only HNO3 at the same conditions. Additionally, a time reduction of up to three-fold was achieved compared to typically demanding edible oil digestions. The proposed method allowed the determination of As, Cd, Cr, Mn, Ni, and Pb in edible vegetable oil samples by ICP-MS. Accuracy was evaluated against the reference method, and no significant difference was observed (p = 0.05), with wide linear ranges and good linearity (r ≥ 0.999) and LOD ranging from 0.48 (As) to 2.41 (Cd) µg L-1.

Tube-in-tube membrane photoreactor as a new technology to boost sulfate radical advanced oxidation processes.

This work proposes a tube-in-tube membrane photoreactor, operated in a continuous-mode, to boost the efficiency of peroxydisulfate (PDS), through the photolytic (UV-C radiation) and photocatalytic (TiO2-P25) processes. This new technology can efficiently facilitate the transportation of PDS to the catalyst surface and water to be treated. The ultrafiltration tubular ceramic membrane was used as support for the TiO2-P25 and oxidant-catalyst/water contactor. Tests were performed using a synthetic solution and a municipal secondary effluent, both spiked with a pharmaceutical mix solution (paracetamol (PCT), furosemide (FRS), nimesulide (NMD), and diazepam (DZP); 200 µg L-1 of each). At steady-state regime, the UVC/S2O82-/TiO2 system, with radial PDS addition, showed the highest removal of pharmaceuticals in both matrices. Furthermore, twenty-two transformation products (TPs) were identified by applying LC-QTOF MS technique. Hence, the transformation pathways including hydroxylation in aromatic moiety by an electrophilic attack, electron transfer reactions, cleavage of C-O, C-N bond, H-abstraction and ring opening were proposed. TPs chemical structures were evaluated by in silico (Q)SAR approach using TOXTREE and EPI Suite™ software.

Persulfate mediated solar photo-Fenton aiming at wastewater treatment plant effluent improvement at neutral PH: emerging contaminant removal, disinfection, and elimination of antibiotic-resistant bacteria.

This work investigated an innovative alternative to improve municipal wastewater treatment plant effluent (MWWTP effluent) quality aiming at the removal of contaminants of emerging concern (caffeine, carbendazim, and losartan potassium), and antibiotic-resistant bacteria (ARB), as well as disinfection (E. coli). Persulfate was used as an alternative oxidant in the solar photo-Fenton process (solar/Fe/S2O82-) due to its greater stability in the presence of matrix components. The efficiency of solar/Fe/S2O82- at neutral pH using intermittent iron additions is unprecedented in the literature. At first, solar/Fe/S2O82- was performed in a solar simulator (30 W m-2) leading to more than 60% removal of CECs, and the intermittent iron addition strategy was proved effective. Then, solar/Fe/S2O82- and solar/Fe/H2O2 were compared in semi-pilot scale in a raceway pond reactor (RPR) and a cost analysis was performed. Solar/Fe/S2O82- showed higher efficiencies of removal of target CECs (55%), E. coli (3 log units), and ARB (3 to 4 log units) within 1.9 kJ L-1 of accumulated irradiation compared to solar/Fe/H2O2 (CECs, 49%; E. coli, 2 log units; ARB, 1 to 3 log units in 2.5 kJ L-1). None of the treatments generated acute toxicity upon Allivibrio fischeri. Lower total cost was obtained using S2O82- (0.6 € m-3) compared to H2O2 (1.2 € m-3). Therefore, the iron intermittent addition aligned to the use of persulfate is suitable for MWWTP effluent quality improvement at neutral pH.

A comparative study of persulfate activation by iron-modified diatomite and traditional processes for the treatment of 17α-ethinylestradiol in water.

Emerging pollutants have been the subject of worldwide study because their continuous entry into the environment presents a risk to ecosystems and human health. Advanced oxidation processes show promise for eliminating or reducing the concentrations of emerging pollutants in water. This study aimed to investigate the treatment of aqueous systems containing the synthetic hormone 17α-ethinylestradiol. An innovative method for persulfate activation catalysed by iron-modified diatomite (heterogeneous system) was compared to conventional homogeneous activation methods (iron activation, alkaline activation, and heat activation). Iron-modified diatomite was more efficient in activating persulfate than traditional processes, achieving 98% of pollutant removal. Experimental results indicated that the catalyst can be reused without loss of removal efficiency, with potential environmental and economic benefits.

The synergic persulfate-sodium dodecyl sulfate effect during the electro-oxidation of caffeine using active and non-active anodes.

It has previously been established during the elimination of organic matter that the addition of sodium dodecyl sulfate in solution is an important condition in the electrochemical oxidation approach that allows to increase the production of persulfate, enhancing the efficacy of the treatment. This outcome was observed when using the anodic oxidation with boron doped diamond (BDD), the extra production of persulfate was achieved after the SDS-sulfate released in solution and it reacts with hydroxyl radicals electrogenerated at BDD surface. However, this effect was not already tested by using active anodes. For this reason, the effect of sodium dodecyl sulfate (SDS) during the electrochemical treatment of caffeine was investigated by comparing non-active and active anodes performances. A significant decrease on the oxidation efficiency of caffeine was observed by using Ti/IrO2-Ta2O5 anode at high current density when SDS was added to the solution. Conversely, at BDD anode, the presence of SDS enhanced the degradation efficiency, depending on the applied current density. This behavior is mainly due to the degradation of SDS molecules, which allows to increase the amount of sulfate in solution, promoting the production of persulfate via the mechanism involving hydroxyl radicals when BDD is used. Meanwhile, no oxidation improvements were observed when Ti/IrO2-Ta2O5 anode was employed, limiting the caffeine oxidation. Results clearly showed that the surfactant concentration had little influence on the degradation efficiency, but this result is satisfactory for the BDD system, since it demonstrates that effluents with complex matrices containing surfactants could be effectively degraded using the electrooxidation technique. Degradation mechanisms were explained by electrochemical measurements (polarization curves) as well as the kinetic analysis. Costs and energy consumption were also evaluated.

Degradation of ciprofloxacin using a low-grade titanium ore, persulfate, and artificial sunlight.

In this study, the magnetic fraction (MF) of a low-grade titanium ore (TO) was successfully used as an alternative Fe2+ source in five reuse cycles, in combination with persulfate (PS) and simulated sunlight (SSL) for the degradation of ciprofloxacin (CIP). The best response of the CIP initial concentration, irradiation time, and doses of MF and PS to degrade completely this pollutant were determined based on an experimental design. However, the individual application of MF, PS, or SSL fails to achieve this goal at the optimal experimental condition. Furthermore, the MF-PS-SSL system showed a higher production of sulfate radicals and a concentration of dissolved Fe2+ ions compared with data obtained for the MF-PS system. The best performance attained by the former system is due to the synergy produced between the photo-generated electrons, and the reaction of PS with the Fe2+ ions leached gradually from the MF, which increased sulfate radical production. After five reuse cycles of the MF, the oxidation system showed a CIP degradation of 100% in 100 min, no residual content of PS, a CIP mineralization of 6%, a marginal increase in the biodegradability (BOD5/COD ratio), a MF loss of 7.5%, and a twofold increase in toxicity; however, this parameter was lower than the effective concentration at 50% inhibition (EC50). The substitution of MF with an iron salt decreased the degradation efficiency of the antibiotic by 14%, probably owing to the immediate excess of Fe2+ in the solution, which can be oxidized to Fe3+ ions, and as a consequence of this, the production rate of the sulfate radical was also reduced.

Ultraviolet light-mediated activation of persulfate for the degradation of cobalt cyanocomplexes.

The ultraviolet light activation of persulfate (PS) was evaluated for the degradation of cobalt cyanocomplexes, which are considered as some of the most recalcitrant compounds present in mining wastewater. The influence of the solution pH (11 and 13), initial concentration of PS (0.1, 0.3, 0.5, 0.7 and 0.9 g/L), dissolved oxygen and initial concentration of contaminant were evaluated. Photolysis results showed that [Formula: see text] is photosensitive to UVC radiation, while the activation of PS by alkaline pH does not contribute to the degradation of the cyanocomplex. There was no presence of CN- at both solution pH values using UVC/PS. But at pH 13, the degradation of cobalt cyanocomplexes and the pseudo-first-order rate constant increased. This was attributed to the effective conversion of SO4•- to HO• and to the increase in the oxidative photolysis of PS at high pH. Additional tests demonstrated better performance of UVC/PS in the absence of oxygen which may be caused by the quenching effect of O2 to the higher energy excited state of the cyanocomplex that must be reached to initiate degradation reactions. Increasing the initial concentration of [Formula: see text] will increase the amount of Co removed but it represents the higher specific energy consumption.

Comparison between UVA- and zero-valent iron-activated persulfate processes for degrading propylparaben.

Conventional wastewater treatments are not efficient in removing parabens, which may thus end up in surface waters, posing a threat to aquatic biota and human health. As an alternative treatment, persulfate (PS)-driven advanced oxidation technologies have gained growing attention for removing these pollutants. In this study, the degradation of propylparaben (PrP) by UVA- and zero-valent iron (ZVI)-activated persulfate was investigated. The effects of initial PS concentration ([PS]0) and irradiance or ZVI concentration were explored using the Doehlert experimental design. For the UVA-activated system, the specific PrP degradation rate (k) and percent removal were consistently higher for increasing [PS]0 and irradiance, varying in the ranges 0.0053-0.0192 min-1 and 37.9-77.3%, respectively. In contrast, extremely fast PrP degradation was achieved through the ZVI/PS process (0.3304 < k < 0.9212 min-1), with removal percentages above 97.5%; in this case, paraben degradation was hindered for a ZVI dosage beyond 40 mg L-1. Regarding toxicity, ECOSAR predictions suggest that the degradation products elucidated by LC-MS/MS are less toxic than PrP toward fish, daphnid, and green algae. In addition, both processes showed to be strongly dependent on the water matrix, being ZVI/PS more impacted for a MBR effluent, although its performance was much better than that exhibited by the UVA-driven process (t1/2 of 65.4 and 276.1 min, respectively).

Dataset of the efficiency of the ultraviolet light activation of persulfate ion for the degradation of cobalt cyanocomplexes in synthetic mining wastewater.

In recent years, the extraction of gold has become important for the development of nations. However, mining wastewater represents an environmental problem due to its high content of free cyanide-based compounds and weak and strong cyanocomplexes for the use of sodium cyanide to obtain gold from minerals. The experimental data presented show the performance of the elimination of one of the strongest cyanocomplex that can appear in mining wastewater ( [ Co ( CN ) 6 ] 3 - ) by the ultraviolet C activation of persulfate (PS). The removal of total cobalt in solution was used as an indicator of the elimination of the cobalt cyanocomplexes that appear as transformation products from the degradation of [ Co ( CN ) 6 ] 3 - . The data evidence that strong cyanocomplexes can be eliminated from mining wastewater. The experimental runs were divided into two parts: as a first step, the influence of the UVC light was elucidated. Afterward, five initial concentrations of persulfate ion (0.1, 0.3, 0.5, 0.7 and 0.9 g/L of PS), two pH values (11 and 13) and two additional initial concentrations of contaminant (25 mg/L and 75 mg/L of [ Co ( CN ) 6 ] 3 - ) were examined to find the optimal parameter where the highest Co removal is obtained.

How does intensification influence the operational and environmental performance of photo-Fenton processes at acidic and circumneutral pH.

This study evaluates the technical, economical, and environmental impact of sodium persulfate (Na2S2O8) as an enhancing agent in a photo-Fenton process within a solar-pond type reactor (SPR). Photo-Fenton (PF) and photo-Fenton intensified with the addition of persulfate (PFPS) processes decolorize 97% the azo dye direct blue 71 (DB71) and allow producing a highly biodegradable effluent. Intensification with persulfate allowed reducing treatment time in 33% (from 120 to 80 min) and the consumption of chemical auxiliaries needed for pH adjustment. Energy, reagents, and chemical auxiliaries are still and environmental hotspot for PF and PFPS; however, it is worth mentioning that their environmental footprint is lower than that observed for compound parabolic concentrator (CPC)-type reactors. A life-cycle assessment (LCA) confirms that H2O2, NaOH, and energy consumption are the variables with the highest impact from an environmental standpoint. The use of persulfate reduced the relative impact in 1.2 to 12% in 12 of the 18 environmental categories studied using the ReCiPe method. The PFPS process emits 1.23 kg CO2 (CO2-Eqv/m3 treated water). On the other hand, the PF process emits 1.28 kg CO2 (CO2-Eqv/m3 treated water). Process intensification, chemometric techniques, and the use of SPRs minimize the impact of some barriers (reagent and energy consumption, technical complexity of reactors, pressure drops, dirt on the reflecting surfaces, fragility of reactor materials), limiting the application of advanced oxidation systems at an industrial level, and decrease treatment cost as well as potential environmental impacts associated with energy and reagents consumption. Treatment costs for PF processes (US$0.78/m3) and PFPS processes (US$0.63/m3) were 20 times lower than those reported for photo-Fenton processes in CPC-type reactors.

Strategies for oxidation of PAHs in aged contaminated soil by batch reactors.

Polycyclic aromatic hydrocarbons (PAH) are neutral, nonpolar and hydrophobic molecules that tend to sorb onto soil organic matter. Chemical oxidation is a good choice to avoid the limitations of bioremediation. To evaluate the efficiency of different types of oxidation (permanganate, hydrogen peroxide, and persulfate) and activation (heat, alkaline, and iron), batch reactors were prepared. The soil was contaminated with phenanthrene and pyrene (1200 ± 200 and 2800 ± 100mg per kg of dry soil, respectively) and aged for fifteen months. Treatments were prepared with 10g of contaminated dry soil and 20ml of water and incubated at room temperature for 7 days. Analyses of phenanthrene and pyrene concentrations, soil pH and electric conductivity were performed. Counts of heterotrophic cultivable bacteria on R2A medium and PAH-degraders were carried out after 7 days of treatment. The persulfate treatment at room temperature, without the addition of activators, achieved better results than treatments with the same doses of permanganate or hydrogen peroxide. All the strategies to improve persulfate treatments yielded higher degradation of pyrene than the biological control, as expected from the structural description of this compound by Clar's model. The thermal activation of persulfate (65°C for 6h) led to the degradation of more than 90% of both PAHs after 7 days of treatment.