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The olive mill industry is a relevant sector in the economy of Mediterranean countries, while it involves high consumption of water and the production of effluents with high environmental impact. The efficient treatment of olive mill wastewater (OMW) is of high relevance, particularly for these countries. Climate changes are leading to increasing periods of droughts, and water recovery from polluted streams is essential to ensure the sustainability of this scarce resource. A combination of various technologies involving physical, chemical, and biological processes has been developed for OMW treatment. However, the treatments studied have limitations such as the operation costs, difficulty of industrial scale-up, and the fact that the vast majority do not lead to suitable treated water for discharge/reuse. As such, it is urgent to develop a solution capable of efficiently treating this effluent, overcoming the disadvantages of existing processes to convert OMW from a serious environmental problem into a valuable source of water and nutrients. In this review, several studies based on the OMW treatment are critically discussed, from conventional approaches such as the physical (e.g. centrifugation, filtration, and adsorption) and biological (anaerobic digestion and anaerobic co-digestion) processes, to the most recent technologies such as advanced membrane filtration, advanced oxidation processes (AOPs) and sulfate radical based AOPs (SR-AOPs). Due to the complexity of the effluent, OMW cannot be efficiently treated by a single process, requiring a sequence of technologies before reaching the required characteristics for discharge into water courses or use in crop irrigation. Reviewing the published results in this matter, it seems that the sequence of processes encompassing ozonation, anaerobic digestion, and SR-AOPs could be the ideal combination for this purpose. However, membrane technologies may be necessary in the final stage of treatment so that the effluent meets legal discharge or irrigation limits., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier B.V. All rights reserved.)

Photosensitization, a powerful oxidation reaction, offers significant potential for wastewater treatment in the context of industrial process water reuse. This environmentally friendly process can be crucial in reducing water consumption and industrial pollution. The ultimate goal is to complete process water reuse, creating a closed-loop system that preserves the inherent value of water resources. The photosensitized oxidation reaction hinges on three essential components: the photosensitizer, visible light, and oxygen. In this study, we assess the performance of three distinct materials-silica, chitosan, and spongin-as carrier materials for incorporating the phthalocyanine photosensitizer (ZnPcS 4 ) in the heterogenous photosensitization process. Among the three materials under study, chitosan emerged as the standout performer in reactor hydrodynamic performance. In the photooxidation process, the photosensitizer ZnPcS 4 exhibited notable efficacy, resulting in a significant reduction of approximately 20 to 30% in the remaining COD concentration of the cellar wastewater. Chitosan demonstrated exceptional hydrodynamic characteristics and displayed a favorable response to pH adjustments within the range of 8 to 10, outperforming the other two carrier materials. To further enhance the efficiency of continuous operation, exploring methods for mitigating photosensitizer bleaching within the reaction medium and investigating the impact of different pH values on the process optimization would be prudent., (© 2023. The Author(s).)

Untreated swine wastewater (SW) discharge leads to serious consequences such as water quality decreasing related to eutrophication and proliferation of harmful algae containing cyanotoxins, which can cause acute intoxication in humans. The use of untreated pig farming effluent as fertilizer can lead to the accumulation of polluting compounds. Biological treatments can degrade organic matter but have the disadvantage of requiring large areas and high retention times and demonstrating low efficiencies in the degradation of refractory compounds such as pharmaceutical compounds. In this ambit, the performance of four low-cost materials was evaluated for treatment of a swine wastewater using physical-chemical processes such as adsorption and Fenton's process. The tested materials are two natural resources, red volcanic rock from Canary (RVR) Islands and black volcanic rock (BVR) from Azores, and two industry residues, red mud (RM) and iron filings (IF). Among the tested materials, only IFs are catalytically active for Fenton's peroxidation. Still, RVR, BVR, and RM were efficient adsorbents removing up to 67% of COD. The combination between adsorption followed by Fenton's process using IF as catalyst showed interesting results. When RM is applied as adsorbent in the diluted effluent, it was able to remove 67% and 90% of COD for adsorption and adsorption followed by IF Fenton, respectively. At those conditions, the resultant treated effluent accomplishes the requirements for direct discharge in the natural water courses as well as the parameters for water reusing., (© 2023. The Author(s).)

The efficiency of ozonation depends on the water matrix and the reaction time. Herein, these factors were addressed by assessing the removal of five pharmaceutical and personal care products (PPCPs) by ozonation. The main aims were: (i) to assess the effects of the water matrix on the degradation kinetics of PPCPs, individually and in mixture, following ozonation; and (ii) to assess the ecotoxicological impact of the ozone reaction time on the treatment of a spiked municipal wastewater (MW) added the five PPCPs over several species. The degradation of the PPCPs was faster in ultrapure water, with all PPCPs being removed in 20 min, whereas in the MW, a 30 min ozonation period was required to achieve a removal close to 100%. Increasing the number of PPCPs in the water matrix did not affect the time required for their removal in the MW. Regarding the ecotoxicity assessment, Raphidocelis subcapitata and Daphnia magna were the least sensitive species, whereas Lemna minor was the most sensitive. The temporal variation of the observed effects corroborates the degradation of the added PPCPs and the formation of toxic degradation by-products. The removal of the parent compounds did not guarantee decreased hazardous potential to biological species.

The water scarcity, the presence of different contaminants in the worldwide waters and wastewaters and their impacts should motivate their good elimination and water management. With this, photocatalysis and photocatalytic ozonation are strong solutions to obtain good quality reclaimed water, for different applications. Nanostructured supported photo-active catalysts, such as the TiO 2 , WO 3 or ZnO can positively affect the performance of such technologies. Therefore, different semiconductors materials have been aroused the interest of the scientific community, mainly due to its functional properties as well as characteristics imposed by the different nanostructures. With this, this work overviews different works and perspective on the TiO 2 nanotubes and other semiconductors nanostructures, with the analysis of different works from 2001 to 2022. Aspects as the substrate effect, electrolyte nature, aspect ratio, electrolyte aging, and annealing treatment but also the effect of morphology, anodization time, applied voltage, temperature and viscosity are discussed. Modification of TiO 2 nanotubes is also presented in this paper. The main objective of this work is to present and discuss the key parameters and their effects on the anodization of different semiconductors, as well as the results obtained until today on the degradation of different contaminants by photocatalysis and photocatalytic ozonation, as well as their use on the treatment of real wastewater. TiO 2 nanotubes present unique properties and highly ordered configuration, which motivate their use on photo-driven technologies for the pollutant's abatement, even when compared to other nanostructures. However, photocatalysts with activity on the visible range and solar radiation, such as the WO 3 , can present higher performance and can decrease operational costs, and must be an important source and a key to find efficient and cost-friendly solutions., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Agro-industrial wastewater management becomes a major task while environmental regulations are becoming stricter worldwide. Agro-industrial wastewaters are known by high content of organic pollutants that cause an adverse effect on the water bodies. Industries are looking for efficient, easy-to-use and affordable treatment processes. Sulfate radical based advanced oxidation processes (S-AOPs) are arising as suitable alternatives for agro-industrial effluents treatment. In this review, the major findings regarding the application of this technology for real agro-industrial wastewater depuration are discussed. Moreover, these technologies are compared as an alternative to Fenton's process, which is a widely studied advanced oxidation process and with high efficiency in the treatment of agro-industrial effluents. The studies already carried out are promising, but there is still a great lack of studies in this area and using this technique., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)

The application of TiO 2 as a slurry catalyst for the degradation of contaminants of emerging concern (CEC) in liquid effluents has some drawbacks due to the difficulties in the catalyst reutilization. Thus, sophisticated and expensive separation methods are required after the reaction step. Alternatively, several types of materials have been used to support powder catalysts, so that fixed or fluidized bed reactors may be used. In this context, the objective of this work is to systematize and analyze the results of research inherent to the application of ceramic materials as support of TiO 2 in the photocatalytic CEC removal from liquid effluents. Firstly, an overview is given about the treatment processes able to degrade CEC. In particular, the photocatalysts supported in ceramic materials are analyzed, namely the immobilization techniques applied to support TiO 2 in these materials. Finally, a critical review of the literature dedicated to photocatalysis with supported TiO 2 is presented, where the performance of the catalyst is considered as well as the main drivers and barriers for implementing this process. A focal point in the future is to investigate the possibility of depurating effluents and promote water reuse in safe conditions, and the supported TiO 2 in ceramic materials may play a role in this scope.

Functional organic dyes play a key role in many fields, namely in biotechnology and medical diagnosis. Herein, we report two novel 2,3- and 3,4-dihydroxyphenyl substituted rosamines ( 3 and 4 , respectively) that were successfully synthesized through a microwave-assisted protocol. The best reaction yields were obtained for rosamine 4 , which also showed the most interesting photophysical properties, specially toward biogenic amines (BAs). Several amines including n - and t -butylamine, cadaverine, and putrescine cause spectral changes of 4 , in UV-Vis and fluorescence spectra, which are indicative of their potential application as an effective tool to detect amines in acetonitrile solutions. In the gas phase, the probe response is more expressive for spermine and putrescine. Additionally, we found that methanolic solutions of rosamine 4 and n -butylamine undergo a pink to yellow color change over time, which has been attributed to the formation of a new compound. The latter was isolated and identified as 5 (9-aminopyronin), whose solutions exhibit a remarkable increase in fluorescence intensity together with a shift toward more energetic wavelengths. Other 9-aminopyronins 6a , 6b , 7a , and 7b were obtained from methanolic solutions of 4 with putrescine and cadaverine, demonstrating the potential of this new xanthene entity to react with primary amines.

The olive mill wastewaters obtained from two different processes, press extraction olive mill wastewater (POMW) from Portugal and two-phase system olive mill wastewater (2POMW) from Spain, were treated to recover phenolic compounds and water sequentially, by the integration of liquid-liquid extraction with Fenton's processes. From the recovered fractions, squalene, oleic acid, tyrosol, syringic acid, and p-coumaric acid were identified, and oleic acid appears in a higher concentration for 2POMW wastewater for all used solvents compared to POMW samples. Recovered fractions presented higher antioxidant activity, but remained antioxidants were found in the residual water. The wastewaters coming from a two-phase extraction method (2POMW) present higher phytotoxicity according to germination index, but the application of Fenton's process was able to improve the water quality to be re-used since an increase on the water biodegradability (BOD5/COD) and toxicity reduction were achieved.

Titanium dioxide can present advantages when coupled with ozonation. Moreover, the catalytic ozonation can be enhanced by radiation. The main disadvantage of this technology is the use of a suspended catalyst entailing a separation step. Thus, catalytic ozonation was analysed using supported TiO 2 nanotubes prepared by anodization at different voltages. The effect of different radiation sources on the catalytic ozonation of parabens was tested. The increase on voltage preparation led to plates with higher surface areas from 60 to 280 cm 2 . However, this did not improve the parabens mixture degradation during UVA photocatalytic ozonation. The use of sunlight radiation allows a significant reduction in terms of time necessary for total parabens degradation from 15 to 10 min. However, the amount of ozone required doubles. Catalytic ozonation presents worst results than single ozonation. This means that molecular ozone is the main responsible for degradation. No dissolved ozone was detected at the experiments with supported nanotubes which could mean that it was adsorbed on the catalysts surface decreasing the degradation rates. The presence of municipal wastewaters as matrix inhibited parabens degradation for both single and catalytic ozonation, mainly due to the trapping ozone effect. In fact, for the TOD of 4.5 mg/L it was just possible to remove about 80% of parabens when MWW compared to 100% when UP was used. Even so, the presence of supported nanotubes during ozonation seems to be required to reduce the toxicity of the resultant treated effluent. In fact, the wastewater luminescence inhibition decreased (from 100 to 43%) and germination index increased (from 7 to 97%) with catalytic ozonation which may enable treated water reuse., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

The classification of wastes regarding hazardous property HP 14 (ecotoxicity) is essential for proper waste management. In the EU, HP 14 has been estimated based on waste chemical composition rather than using biotests, and guidelines for experimental assessment are still lacking. This study aims at evaluating the potential ecotoxicological impacts of weathered coal fly ash (CFA) from a landfill, as a case study to assess the current EU methodology used to classify wastes regarding HP 14. A large amount of CFA is still landfilled, but its valorisation would be of interest. The analysis was based on the chemical composition of CFA (in ClassifyMyWaste software), and on a battery of five biotests applied to eluates, with Lepidium sativum, Aliivibrio fischeri, Raphidocelis subcapitata, Lemna minor and Daphnia magna. Through chemical analysis, most of the simulations with data from the literature indicated "Possible Hazard", including the sample of this work. Biotests revealed low impairment for most endpoints. D. magna was the most sensitive organism, but the inhibitory effect was significantly reduced after pH adjustment of the eluate. The test with A. fischeri does not seem to be adequate to assess CFA due to the high variability observed in results. The methodology involving a simple battery of bioassays was proven to be enlightening, providing relevant results for HP 14 assessment. The chosen battery of biotests (excluding the A. fischeri test) may be a good starting point to represent the aquatic environment in this context. In short, it seems that weathered CFA can be considered non-hazardous, and therefore the material under analysis could be valorised in practical applications without significant ecotoxic effect on the environment.

Nitrogen-doped TiO 2 was applied in photocatalytic ozonation reactions for the degradation of a mixture of five parabens under UVA radiation, being evaluated the influence of the reaction medium. The initial mixture parabens concentration considered in these experiments was 50 mg L -1 . The parabens degradation rate was considerably enhanced under neutral pH, specially using a buffered solution, leading to a complete removal under 60 min and with transferred ozone dose (TOD) 36% lower compared to reaction under natural conditions. Isopropanol, known radical scavenger, impeded the complete contaminants removal, affecting the reaction route and by-products formation, but when KI was jointly added, total removal was achieved under 30 min and with a TOD of 25.9 mg L -1 . Parabens depletion was also improved in the presence of Cl - , SO 4 2- and HCO 3 - , commonly present in wastewaters. The use of river water (RW) and a secondary wastewater (SWW) as water matrices maintained the process efficiency with lower TOD required, and treated solutions presented lower phytotoxicity towards Lepidium sativum., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Wastewater treatment plants are not specially designed to remove pharmaceutically active compounds (PhACs), since these substances are toxic and bio-refractory. This paper aims to investigate and optimize the performance of the Trisep TS80 nanofiltration (NF) membrane for the removal of a mixture of two of the most detected PhACs in municipal wastewaters worldwide, sulfamethoxazole and diclofenac. Several NF tests were carried out to study the rejections of these contaminants both spiked in demineralized water, filtrated water taken from Mondego River and secondary effluent coming from a municipal wastewater treatment plant. Among the several studied operating variables, pH was the one that most affected the contaminant rejection and membrane permeability. In the case of synthetic effluent, an applied pressure of 10 bar and pH 7 were determined as the best operating conditions, which allowed almost total chemical oxygen demand retention and a global contaminant rejection of 96.3% to be achieved. The application of different water matrices (river water and secondary municipal effluent) had no relevant impact on process efficiency. Vibrio fischeri luminescence inhibition tests revealed that treatment by nanofiltration reduced acute toxicity of all studied effluents.

Parabens (esters of p-hydroxybenzoic acid) are xenobiosis belonging to endocrine disruptors and commonly used as a preservative in cosmetics, food, pharmaceutical, and personal care products. Their wide use is leading to their appearance in water and wastewater in the range from ng/L to mg/L. In fact, the toxicity of benzylparaben is comparable to bisphenol A. Therefore, it is important to find not only effective but also ecofriendly methods for their removal from aqueous environment since the traditional wastewater treatment approaches are ineffective. Herein, for the first time, such extended comparison of several radical-driven technologies for paraben mixture degradation is presented. The detailed evaluation included (1) comparison of ozone and hydroxyl peroxide processes; (2) comparison of catalytic and photocatalytic processes (including photocatalytic ozonation); (3) characterisation of catalysts using SEM, XRD, DRS, XPS techniques and BET isotherm; (4) mineralisation, biodegradability and toxicity assessment; and (5) cost assessment. O 3 , H 2 O 2 /Fe 2+ , H 2 O 2 /UVC, O 3 /H 2 O 2 , O 3 /UVA, O 3 /H 2 O 2 /UVA, UVA/catalyst, O 3 /catalyst and O 3 /UVA/catalyst were selected from advanced oxidation processes to degrade parabens as well as to decrease its toxicity towards Aliivibrio fischeri, Corbicula fluminea and Lepidium sativum. Research was focused on the photocatalytic process involving visible light (UVA and natural sunlight) and TiO 2 catalysts modified by different metals (Ag, Pt, Pd, Au). Photocatalytic oxidation showed the lowest efficiency, while in combining ozone with catalysis and photocatalysis process, degradation efficiency and toxicity removal were improved. Photocatalytic ozonation slightly improved degradation efficiency but appreciably decreased transferred ozone dose (TOD). Results indicate that the degradation pathway is different, or different transformation products (TPs) could be formed, despite that the hydroxyl radicals are the main oxidant. Graphical abstract.

Self-organized TiO 2 nanotubes as immobilized photocatalysts were evaluated in detail for the photocatalytic degradation of parabens mixtures from ultrapure water. This kind of approach can be a very suitable option for emerging contaminants degradation considering the possibility of the catalyst reuse and recovery which will be simpler than when catalytic powders are used. The anodization method was applied for the TiO 2 nanotubes production under different preparation voltages (20, 30 and 40 V). These preparation conditions are important on the morphological characteristics of nanotubes such as length, as well as internal and external diameters. The photocatalytic efficiency was dependent on the materials preparation voltages. The photocatalytic oxidation was evaluated using two different irradiation sources, namely UVA and sunlight. These irradiation sources were evaluated for parabens mixture degradation using different number of catalytic plates. The increase of the number of plates improved the parabens degradation possibly due to the availability of more active sites which can be relevant for the hydroxyl radical's generation. The effect of the reactor design was also evaluated using sunlight irradiation. The configuration, position and solar concentrators can be important for the performance of degradation. The mechanism of degradation was analysed through by-products formation under sunlight irradiation. The main responsible for parabens degradation was hydroxyl radical. Decarboxylation, dealkylation and hydroxylation seem to be the most important reactional steps for the mixture decontamination., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Parabens are widely used as antimicrobial and preservative in pharmaceutical and personal products. Their presence has been detected in rivers and wastewater treatment plants. Photocatalytic ozonation process using a low amount of 0.1 wt% Ag-TiO 2 proved to be efficient on the degradation of a mixture of five parabens using a low transferred ozone dose (TOD). The pH effect was analyzed under acidic and neutral conditions. Also, the effect of hydroxyl radical scavenger on parabens degradation and on by-products formation was discussed. Hydroxyl radical present a significant role over parabens degradation and also on by-products formation. The reaction mechanism was analyzed using municipal wastewater as a matrix to infer about the behavior of the process at actual conditions. Municipal wastewater as a matrix clearly enhanced the parabens degradation when compared with the case where ultrapure water was used. In fact, the TOD required for total parabens degradation is lowered 10-20 mg/L of TOD. Therefore, to understand the main responsible species for this improvement, the effects of several ions naturally present in wastewater (HCO 3 - , Cl - and SO 4 2- ) were tested. According to the results it seems that sulfate radical improves the process, while chloride and bicarbonate radicals decrease the process efficiency. In terms of toxicity the luminescence inhibition for Vibrio fischeri was analyzed. The inhibition significantly decreased for treated spiked municipal wastewater., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Corbicula fluminea, an Asian clam, is one of the worst invasive species in Europe that can survive in very adverse environmental conditions. Despite its negative impacts, the species also has the capacity to bioaccumulate heavy metals, contaminants and can be exploited for wastewater treatment purposes. The capacity of the Asian clam to remove Escherichia coli, used as fecal contamination indicator, was analyzed. Conventional wastewater treatment plants are not suitable to remove bacteria, thus resulting in treated municipal wastewater with high bacterial loads. E. coli clearance rate was analyzed as function of the number of clams. The bivalves can remove bacteria until concentrations below the detection limit in about 6 h. The adsorption on the clam shells' and bioaccumulation on the soft tissues were also analyzed. The depuration of clams along 48 h were analyzed revealing that no bacteria was detected in the water. Thus, these results suggest that Asian clam can bioprocess E. coli. On the other hand, results obtained by this methodology were compared with ozonation and photocatalytic oxidation using TiO 2 , Ag, Au, Pd-TiO 2 . In all treatments it was possible to achieve concentrations of E. coli below the detection limit. However, photocatalytic oxidation demands about 4700 folds more energy than ozonation, besides the costs associated with catalysts. Comparing complexity of ozonation with biofiltration, this study suggests that application of biofiltration using C. fluminea can be a suitable solution to minimize the presence of bacteria in wastewater, reducing environmental and economic impacts., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

The main goal of this work was to assess the performance of an integrated membrane system for the treatment and valorization of wastewater generated from an olive mill (OMW) coming from a traditional extraction press. Two different lots of this effluent were firstly processed in an ultrafiltration (UF) pilot unit after a pretreatment by screening. The effect of transmembrane pressure (TMP) and temperature on the chemical oxygen demand (COD) reduction and removal of total phenolic (TPh) content was investigated. Under optimal conditions (TMP = 1.5 bar and T = 20 °C), 20.6 and 26.8% for COD and TPh removal were achieved, respectively. The permeate from UF was then treated by nanofiltration (NF) in order to obtain a retentate enriched in phenolic compounds. The influence of pressure drop (ΔP), temperature, and pH on the removal of COD, TPh, and permeate flow was examined using a 2 3 full-factorial experimental design. The effect of the independent variables and their interactions on the process performance was analyzed with Pareto charts. Multivariable regression models allowed to built 3D surface plots. The best conditions that maximize the COD abatement (83.3%) and TPh removal (93.1%) were ΔP = 18 bar, T = 20 °C, and a pH 2.7. It can be concluded that the integration of UF and NF processes investigated in this work is a promising strategy for the treatment and valorization of OMW.

The environmental and economic impact of invasive bivalve species implies the development of suitable pest management strategies. Chemical control is the most usual approach. However, the production of toxic intermediates as well as the unavoidable impact over non target biota is of special concern. Another approach consists on the physical removal of the animals from the invaded sites. The high biofiltration and bioaccumulation capacity of such animals make them interesting for the removal of contaminants from water and wastewater. In this context, environmental applications can be given for these pests encompassing nutrients removal for the recovery of eutrophic sites, water disinfection, organic and metal contaminants abatement. These approaches may be integrated with pest management where the physical removed animals from the invaded spots could be used for assembling biofilter for water and wastewater decontamination. However, some drawbacks must be addressed before proposing such alternative. In fact, the further spreading of the bivalves into non-invaded sites must be avoided. Moreover, some operational questions must be addressed such as the fate of contaminated animals after biofiltration. Bearing in mind the interesting results already available in this subject, this paper aims to critically overview literature regarding the environmental applications of invasive bivalves., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Diclofenac (DCF) and Sulfamethoxazole (SMX) are two of the most frequently detected pharmaceutical compounds in water and are hardly removed by biological treatment systems. The presence of H 2 O 2 was investigated in the ozonation of these two compounds. Experiments were carried out with both using distilled water and secondary effluent from a municipal wastewater treatment plant spiked with pharmaceuticals. Chemical oxygen demand (COD) abatement rate improved when H 2 O 2 was added at the beginning of the ozonation process and when the ozone inlet concentration increased, attaining a maximum value of 91% and simultaneously a lower ozone waste for a H 2 O 2 initial concentration of 5 mM and an ozone inlet concentration of 20 g Nm -3 . For these operation conditions, the water matrix has no significant impact on SMX and DCF removal, which were totally degraded in 45 and 60 min, respectively. Nevertheless, lower COD degradation and ozone usage were obtained when the secondary effluent was used. Inorganic ions such as chloride, sulphate and nitrate and short-chain organic compounds were detected as by-products of the SMX and DCF oxidation. Vibrio fischeri luminescence inhibition tests revealed that simultaneous use of ozone and H 2 O 2 reduced acute toxicity.

Parabens are widely used as antimicrobial and preservatives in pharmaceutical and personal care products and are continuously reaching the water streams. Conventional wastewater treatments are proven inefficient on the removal of this kind of contaminants from wastewater. Therefore, catalytic ozonation appears as a suitable option, due to the oxidant power of ozone and its high capacity of hydroxyl radical generation in the presence of a suitable catalyst. The main drawback of catalytic ozonation is related with the choice of stable and active catalysts at low cost. On this way, two volcanic rocks were tested to enhance the removal of a mixture of parabens by ozonation, improving their degradation. Indeed, catalytic ozonation with volcanic rock allowed total paraben degradation using a transferred ozone dose (TOD) of 55 mg/L which corresponds to a reduction of about threefold the amount of TOD comparatively with single ozonation (170 mg/L of TOD). Due to the presence of semiconductors on volcanic rock composition, the effect of UVA irradiation on paraben degradation was analyzed. The neutral and basic conditions enhanced catalytic ozonation comparatively to acid conditions. Higher pH values allowed a total methylparaben degradation with 35 mg O 3 /L, whereas for low pH values, 55 mg O 3 /L was required. The use of a radical scavenger proven that hydroxyl radicals are the main responsible for paraben degradation with catalytic ozonation. This was confirmed through the analysis of the by-products, where 4-hydroxybenzoic acid, 3,4-dihydroxybenzoic acid (3,4-diHBA), 2,4-dihydroxybenzoic acid, and hydroquinone were quantified.

Tuberculosis is one of the major public health concerns. This highly contagious disease affects more than 10.4 million people, being a leading cause of morbidity by infection. Tuberculosis is diagnosed at the point-of-care by the Ziehl-Neelsen sputum smear microscopy test. Ziehl-Neelsen is laborious, prone to human error and infection risk, with a limit of detection of 10 4 cells/mL. In resource-poor nations, a more practical test, with lower detection limit, is paramount. This work uses a magnetoresistive biosensor to detect BCG bacteria for tuberculosis diagnosis. Herein we report: i) nanoparticle assembly method and specificity for tuberculosis detection; ii) demonstration of proportionality between BCG cell concentration and magnetoresistive voltage signal; iii) application of multiplicative signal correction for systematic effects removal; iv) investigation of calibration effectiveness using chemometrics methods; and v) comparison with state-of-the-art point-of-care tuberculosis biosensors. Results present a clear correspondence between voltage signal and cell concentration. Multiplicative signal correction removes baseline shifts within and between biochip sensors, allowing accurate and precise voltage signal between different biochips. The corrected signal was used for multivariate regression models, which significantly decreased the calibration standard error from 0.50 to 0.03log 10 (cells/mL). Results show that Ziehl-Neelsen detection limits and below are achievable with the magnetoresistive biochip, when pre-processing and chemometrics are used., (Copyright © 2017 Elsevier B.V. All rights reserved.)

A novel integrated methodology involving Fenton's process followed by ion exchange (IE) was proposed for the treatment of olive mill wastewater. Fenton's process was optimized and it was able to remove up to 81% of chemical oxygen demand when pH 3.5, reaction time 1 h, [Fe 2+ ] = 50 mg L -1 and [Fe 2+ ]/[H 2 O 2 ] = 0.002 were applied. In spite of the potential of this treatment approach, final iron removal from the liquid typically entails pH increase and iron sludge production. The integration of an IE procedure using Lewatit TP 207 resin was found to be able to overcome this important environmental shortcoming. The resin showed higher affinity toward Fe 3+ than to Fe 2+ . However, the iron removal efficiency of an effluent coming from Fenton's was independent of the type of the initial iron used in the process. The presence of organic matter had no significant effect over the resin iron removal efficiency. Even if some efficiency decrease was observed when a high initial iron load was applied, the adsorbent mass quantity can be easily adapted to reach the desired iron removal. The use of IE is an interesting industrial approach able to surpass Fenton's peroxidation drawback and will surely boost its full-scale application in the treatment of bio-refractory effluents.

Conventional wastewater treatments are inefficient for the removal of parabens. The aim of this study was finding a suitable solution using ozone and UVA irradiation combined with TiO 2 catalysts doped with different noble metals (Ag, Pt, Pd, Au). Photocatalytic ozonation required lower amounts of ozone for higher efficiency on the removal of parabens, chemical oxygen demand (COD) and total organic carbon (TOC). The best catalyst for the initial contaminants degradation was 0.5% Ag-TiO 2 leading to total parabens removal using 46mgO 3 /L. Due to the relative low mineralization achieved, the toxicity of the treated solutions was still compared with the initial one over several species (Vibrio fischeri, Lepidium sativum and Corbicula fluminea). All the treatments applied led to a clear decrease on the toxicity compared with initial mixture of parabens. From an economical point of view, it was concluded that the presence of UVA irradiation increased the energy consumption compared with catalytic ozonation with these catalysts but it can decrease the time of reaction. From the by-products analysis, it was concluded that hydroxylation appears to be the most significant reaction pathway and the main responsible for parabens degradation., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Lead is a heavy metal of high impact for the environment as well as for human health, being cause of several diseases. Considering the importance of obtaining an effective treatment for lead removal, a new hybrid material was developed for sorption of Pb 2+ from aqueous solution. The effect of pH, temperature, liquid/solid ratio (g/cm 3 ) and lead concentration on the sorption capacity of yeasts chemically modified with cubic silsesquioxane (YS) was analyzed. Additionally, the toxicity of lead on the neuronal activity was also investigated in order to assess whether the damage caused by the Pb 2+ ion is reversible or not. The YS is highly promissory as sorbent of lead in high concentrations (100 and 500ppm), reaching high efficiency in short contact times (15min), and at the natural pH (4) of the Pb 2+ solution and room temperature. The best sorption obtained was 82% removal and 248mg/g with 500cm 3 /g sorbent, pH 4, room temperature and contact time of 15min. Besides, such high efficiencies are obtained with low quantities of biosorbent, when compared with other similar materials. The impact of lead on neuronal function was studied by measuring autofluorescence signals, associated with changes in cellular metabolism, at the hippocampal CA3 area in brain slices. In this toxicity tests, the effect of low concentrations of lead (1 and 3μM) on neuronal activity was evaluated. After removal of the lead, the irreversibility of the observed changes can be verified, which suggests the existence of neuronal damages., (Copyright © 2017 Elsevier B.V. All rights reserved.)

The main objective of this work is to evaluate the phytotoxicity of olive mill solid wastes (OMW) produced in two different centrifugation technologies and also the toxicity associated with specific phenolic compounds. Two samples of waste were collected in two-phase (2P-OMW) and three-phase (3P-OMW) centrifugation olive oil production processes, and cress bioassays with Lepidium sativum L. were employed to evaluate phytotoxicity. Although both OMW have similar total phenolic content (TPh), results confirmed that 2P-OMW is more phytotoxic than 3P-OMW. When extracts from 2P-OMW at liquid to solid ratio of 10 L kg -1 were applied none of the seeds germinated, i.e. germination index (GI) was 0%, while for 3P-OMW GI was 94.3%. Growth tests in soil and mixtures with OMW also led to more favorable results for 3P-OMW, whereas worse results than those obtained in the control experiments were observed. In order to discriminate the individual influence of eleven phenolic compounds, gallic acid, protocatechuic acid, cinnamic acid, syringic acid, 3,4,5-trimethoxybenzoic acid, 4-hydroxybenzoic acid, vanillic acid, p-coumaric acid, caffeic acid, veratric acid and phenol were tested in the concentration range of 5-500 mg L -1 . Results showed that cinnamic acid is the most phytotoxic, with EC 50 of 60 mg L -1 , which is related with its hydrophobicity. Moreover, increasing -OH and -OCH 3 groups in these molecules seem to reduce phytotoxicity. Tests with a mixture of six phenolic compounds demonstrated there are neither synergistic nor additive effects. The phytotoxicity appears to be determined by the presence of the most lipophilic phenolic molecule., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Due to the shortening on natural water resources, reclaimed wastewater will be an important water supply source. However, suitable technologies must be available to guaranty its proper detoxification with special concern for the emerging pharmaceutical and personal care products that are continuously reaching municipal wastewater treatment plants. While conventional biological systems are not suitable to remove these compounds, ozone, due to its interesting features involving molecular ozone oxidation and the possibility of generating unselective hydroxyl radicals, has a wider range of action on micropollutants removal and water disinfection. This paper aims to review the studies dealing with ozone based processes for water reuse by considering municipal wastewater reclamation as well as natural and drinking water treatment. A comparison with alternative technologies is given. The main drawback of ozonation is related with the low mineralization achieved that may lead to the production of reaction intermediates with toxic features. The use of hydrogen peroxide and light aided systems enhance ozone action over pollutants. Moreover, scientific community is focused on the development of solid catalysts able to improve the mineralization level achieved by ozone. Special interest is now being given to solar light catalytic ozonation systems with interesting results both for chemical and biological contaminants abatement. Nowadays the integration between ozonation and sand biofiltration seems to be the most interesting cost effective methodology for water treatment. However, further studies must be performed to optimize this system by understanding the biofiltration mechanisms., (Copyright © 2017 Elsevier B.V. All rights reserved.)

The discharge of poorly decontaminated winery wastewater remains a serious environmental problem in many regions, and the industry is welcoming improved treatment methods. Here, an innovative decontamination approach integrating Fenton's process with biofiltration by Asian clams is proposed. The potential of this approach was assessed at the pilot scale using real effluent and by taking an actual industrial treatment system as a benchmark. Fenton peroxidation was observed to remove 84% of the effluent's chemical oxygen demand (COD), reducing it to 205 mg L. Subsequent biofiltration decreased the effluent's COD to approximately zero, well below the legal discharge limit of 150 mg L, in just 3 d. The reduction of the effluent's organic load through Fenton's process did not decrease its toxicity toward , but the effluent was much less harmful after biofiltration. The performance of the treatment proposed exceeded that of the integrated Fenton's process-sequencing batch reactor design implemented in the winery practice, where a residence time of around 10 d in the biological step typically results in 80 to 90% of COD removal. The method proposed is effective and compatible with typical winery budgets and potentially contributes to the management of a nuisance species., (Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.)

The electrochemical oxidation (EO) of phenolic wastewaters mimicking olive oil mill effluents was carried out in a batch stirring reactor using Ti/IrO 2 anodes, varying the nature (NaCl and Na 2 SO 4 ) and electrolyte concentration (1.8-20 g L -1 ), current density (57-119 mA cm -2 ) and initial pH (3.4-9). Phenolic content (TPh) and chemical oxygen demand (COD) removals were monitored as a function of applied charge and over time. The nature of the electrolyte greatly affected the efficiency of the system, followed by the influence of the current density. The NaCl concentration and the initial pH influenced the process in a lesser extent. The best operating conditions achieved were 10 g L -1 of NaCl, current density of 119 mA cm -2 and initial pH of 3.4. These parameters led to 100 and 84.8% of TPh and COD removal, respectively. Under these conditions, some morphological differences were observed by SEM on the surface of the anode after treatment. To study the potential toxicity of the synthetic effluent in neuronal activity, this mixture was applied to rat brain slices prior to and after EO. The results indicate that although the treated effluent causes a smaller depression of the neuronal reactive oxygen species (ROS) signal than the untreated one, it leads to a potentiation instead of recovery, upon washout. Furthermore, the purification of a real olive mill wastewater (OMW), with the organic load of the synthetic effluent, using the same optimised operating conditions, achieved total phenolic compounds abatement and 62.8% of COD removal.This study demonstrates the applicability of this EO as a pre-treatment process of a real effluent, in order to achieve the legal limit values to be discharged into natural streams regarding its organic load.

A complete industrial treatment system (involving the integration of coagulation/flocculation and Fenton processes) to depurate real wastewaters coming from two-phase olive oil production mills has been studied. The experimental results indicated that at the end of this combined strategy, involving a primary physical separation stage followed by Fenton's chemical oxidation, chemical oxygen demand (COD) is reduced up to 90% and total polyphenols' concentration is decreased up to 92%. The treated stream biodegradability (BOD5/COD) reached 0.52 and the Total Suspended Solids (TSSs) and Total Dissolved Solids (TDSs) decreased up to 95% and 69%, respectively. Fenton's procedure was optimized bearing in mind the pH adjustment step, different procedures for hydrogen peroxide addition and the use of coagulants instead of the chemical precipitation (by raising pH) to promote iron sludge settling. Our results demonstrated that pH (3.0 ± 0.1) control during the oxidation reaction improves the oxidation efficiency. Moreover, the final NaOH addition is essential to a better sludge formation and consequent precipitation of the residual iron removing also some organic matter.

The aims of the present work were to assess the application of a chemical process to degrade a mixture of parabens and determine the influence of a natural river water matrix on toxicity. Model effluents containing either a single compound, namely methylparaben, ethylparaben, propylparaben, butylparaben, benzylparaben or p-hydroxybenzoic acid, or to mimic realistic conditions a mixture of the six compounds was used. Fenton process was applied to reduce the organic charge and toxic properties of the model effluents. The efficiency of the decontamination has been investigated using a chemical as well as a toxicological approach. The potential reduction of the effluents' toxicity after Fenton treatment was evaluated by assessing (i) Vibrio fischeri luminescence inhibition, (ii) lethal effects amongst freshwater Asian clams (Corbicula fluminea), and (iii) the impact on mammalian neuronal activity using brain slices. From the environmental point of view such a broad toxicity analysis has been performed for the first time. The results indicate that Fenton reaction is an effective method for the reduction of chemical oxygen demand of a mixture of parabens and their toxicity to V. fischeri and C. fluminea. However, no important differences were found between raw and treated samples in regard to mammalian neuronal activity.

The aim of the present work was to compare the potential of iron industry wastes to enhance ozone and hydrogen peroxide action on the degradation of olive mill wastewaters (OMWs). The results attained show a higher efficiency for ozonation using a lower catalyst load. Nevertheless, Fenton's process led to a larger amount of chemical oxidation demand (COD) removed per mole of oxidant applied. It was concluded that hydroxyl radicals are responsible for the pollutant abatement. High eco-toxicity decay was observed after the treatments. Furthermore, a preliminary analysis of the iron shavings' stability was made by reusing it in two feed-batch trials. It was concluded that while activity was maintained for Fenton's, a decrease of about 20% was verified for catalytic ozonation. Comparing these results with the ones obtained for the same processes applied to an actual OMW, a lower percentage of COD abatement was achieved. However, when reporting the amount of COD removed per mole of oxidant used, the difference between effluents are not so high. This should be taken into account when deciding which process should be implemented at an industrial scale. With the outcomes of this research it was possible to conclude that integrating waste management with wastewater treatment was feasible.

The utilization of Fenton's oxidation for the depuration of elderberry juice wastewater was studied. The aim was to select the adequate cost-effective operating conditions suitable to lead to an effluent within the legal thresholds to be discharged into the natural water courses. The treatment efficacy was assessed by chemical oxygen demand (COD), colour, phenolic content and total solids removal besides its ability to improve biodegradability (biochemical oxygen demand (BOD5)/COD). Moreover, the costs of the applied reactants were also considered. Fenton's reaction was able to abate at least 70% of COD (corresponding to a final value below 150 mg O2 L(-1)). Besides, total phenolic content degradation was always achieved. Within these conditions, the resulting effluent is able to be directly discharged into the natural hydric channels. Fenton oxidation could be successfully applied as a single treatment method with a reactant cost of 4.38 € m(-3) ([Fe(2+)] = 20 mmol L(-1), [H2O2] = 100 mmol L(-1), pH = 3 and 4 h of oxidation procedure).

With the objective of reaching suitable techniques for olive mill wastewater treatment, ozonation and ultrafiltration were studied individually and combined. A continuous reactor was run for the treatment of a phenolic mixture mimicking an actual olive mill wastewater (OMW) by ozonation. The effect of the main operating parameters was analysed (pH, liquid flow rate and ozone inlet concentration). The increase of pH and ozone dose improved ozonation efficiency. As expected, the highest residence time led to higher steady-state degradation (35 % of chemical oxygen demand (COD) abatement). Even if the rise on ozone inlet gas concentration was able to remove COD in a higher extent, it should be taken into consideration that with the lowest oxidant load (15 g O3/m(3)), the maximum steady-state biochemical oxygen demand (BOD5)/COD ratio was reached which would reduce the process costs. These operating conditions (pH 9, 1 mL/min of liquid flow rate and 15 g O3/m(3)) were applied to an actual OMW leading to 80 % of phenolic content abatement and 12 % of COD removal at the steady state. Regarding ultrafiltration, it was concluded that the best total phenolic content (TPh) and COD abatement results (55 and 15 %) are attained for pH 9 and using a transmembrane pressure drop of 1 bar. Among the integration schemes that were tested, ultrafiltration followed by ozonation was able to reach 93 and 20 % of TPh and COD depletion, respectively. Moreover, this sequence led to an effluent with a BOD5/COD ratio of about 0.55 which means that it likely can be posteriorly refined in a municipal wastewater treatment plant.

The presence of surfactants in wastewater composition tends to jeopardize the efficiency of the traditional aerobic treatment processes. In this regard, the application of Fenton's reaction and nanofiltration as single processes and integrated (nanofiltration followed by Fenton's process) was investigated on the abatement of a solution containing two surfactants usually found in effluents coming from detergent industry (dodecylbenzene--DDB and sodium lauryl ether sulphate--SLES). The potential of a solid waste (iron shavings) as catalyst in the Fenton's process was evaluated and the reaction system was optimized regarding the key operating parameters (iron and hydrogen peroxide concentration and pH). The highest chemical oxygen demand (COD) degradation (66%) was attained for pH 3, [H2O2] = 32 mM and 50 g/L of iron shavings. Besides, it was concluded that oxidation was due to hydroxyl radicals adsorbed on the metal surface even if bulk interaction between hydrogen peroxide and dissolved iron cannot be neglected. The main variables ruling nanofiltration were evaluated (pH, temperature and cross-flow rate). Eighty-four percent of COD rejection was determined at pH 7.5, cross-flow 14.4 cm3 s(-1), 20 degrees C and 15 bar of pressure drop. Finally, nanofiltration followed by Fenton's process under the best conditions was integrated; however, no significant improvement was attained with 85% of COD being globally removed.

Non-catalytic and catalytic ozonation over Pt/Al2O3 were considered in the treatment of a synthetic effluent composed of six phenolic acids usually present in olive mill wastewaters. In both processes the medium pH affected the rate of ozone decomposition and the formation of hydroxyl radicals. The optimum values were achieved for the catalytic system under pH 7 with 93.0 and 47.7%, respectively, of total phenol content and chemical oxygen demand (COD) removal, after 120 minutes of reaction. For pH 3, the catalytic ozonation followed a free radical pathway perceived by the presence of radical scavengers. No significant structural differences were observed between the fresh and used solid catalyst in X-ray diffraction analysis. Aluminium leaching behaviour was also evaluated at the end of each experiment. Moreover, a sequence of feed-batch trials involving the catalyst reutilization exhibited almost constant activity during the operation time. Eco-toxicological tests were performed for both processes, revealing that the treated effluent still presents some ecological impact, although it is lower than that for the raw wastewater.

This study is focused on the evaluation of the impact of Saccharomyces cerevisiae metabolism in the profile of compounds with antioxidant capacity in a synthetic wine during fermentation. A bioanalytical pipeline, which allows for biological systems fingerprinting and sample classification by combining electrochemical features with biochemical background, is proposed. To achieve this objective, alcoholic fermentations of a minimal medium supplemented with phenolic acids were evaluated daily during 11 days, for electrochemical profile, phenolic acids, and the volatile fermentation fraction, using cyclic voltametry, high-performance liquid chromatography-diode array detection, and headspace/solid-phase microextraction/gas chromatography-mass spectrometry (target and nontarget approaches), respectively. It was found that acetic acid, 2-phenylethanol, and isoamyl acetate are compounds with a significative contribution for samples metabolic variability, and the electrochemical features demonstrated redox-potential changes throughout the alcoholic fermentations, showing at the end a similar pattern to normal wines. Moreover, S. cerevisiae had the capacity of producing chlorogenic acid in the supplemented medium fermentation from simple precursors present in the minimal medium.

Composting is one of the technologies recommended for pre-treating industrial eggshells (ES) before its application in soils, for calcium recycling. However, due to the high inorganic content of ES, a mixture of biodegradable materials is required to assure a successful procedure. In this study, an adequate organic blend composition containing potato peel (PP), grass clippings (GC) and wheat straw (WS) was determined by applying the simplex-centroid mixture design method to achieve a desired moisture content, carbon: nitrogen ratio and free air space for effective composting of ES. A blend of 56% PP, 37% GC and 7% WS was selected and tested in a self heating reactor, where 10% (w/w) of ES was incorporated. After 29 days of reactor operation, a dry matter reduction of 46% was achieved and thermophilic temperatures were maintained during 15 days, indicating that the blend selected by statistical approach was adequate for composting of ES.

Ozonation, catalytic ozonation, Fenton's and heterogeneous Fenton-like processes were investigated as possible pretreatments of a low biodegradable and highly toxic wastewater produced by a detergent industry. The presence of a Mn-Ce-O catalyst in ozonation enhances the biodegradability and improves the degradation at low pH values. However, a high content of carbonyl compounds adsorbed on the recovered solid indicates some limitations for real-scale application. A commercial Fe2O3-MnOx catalyst shows higher activity as well as higher stability concerning carbon adsorption, but the leaching of metals is larger than for Mn-Ce-O. Regarding the heterogeneous Fenton-like route with an Fe-Ce-O catalyst, even though a high activity and stability are attained, the intermediates are less biodegradable than the original compounds, indicating that the resulting effluent cannot be conducted to an activated sludge post-treatment. The highest enhancement of effluent biodegradability is obtained with the classic homogeneous Fenton's process, with the BOD5/COD ratio increasing from 0.32 to 0.80. This process was scaled up and the treated effluent is now safely directed to a municipal wastewater treatment plant.

In this experimental work the ozone action on the depuration of olive oil mill wastewater is studied for different operational conditions based on an actual industrial treatment plant. It was verified that the application of a Mn-Ce-O catalyst prepared at the laboratory, with a Mn/Ce molar proportion of 70/30, enhances the depuration efficiency and the effluent biodegradability. Ozonation operation at the natural pH of the effluent is recommended. Moreover, the integration of the Fenton process as a pretreatment improves the final chemical oxygen demand removal and enables a totally biodegradable effluent to be obtained, as confirmed by respirometric techniques.

A mixture of six phenolic acids, corresponding to an initial TOC of 370 mgC/L, was studied by Fenton's peroxidation aiming to improve the biodegradability of agro-industrial wastewaters. Input operating variables including the concentration of pollutants, iron and hydrogen peroxide as well as the reaction time were used to assess the mineralization degree through a factorial experimental methodology. A TOC removal in the range of 15.0-58.8% was attained within the operational conditions used. A reduced model was achieved using the statistically important independent factors and interactions to predict TOC degradation. On the hydrogen peroxide injection methodology, the results showed that the continuous introduction of small volumes is advantageous when compared with one single addition of the overall volume at the zero reaction time with a mineralization improvement of 11%. The use of FeSO(4).7H(2)O correspondent to a Fe(2+) load of 271 mg; [H(2)O(2)]=488.0 mM, injected in twelve aliquots each 30 min during 6h of reaction reached optimal efficiencies with the parent compounds (quantified by HPLC and the Folin-Ciocalteau method) quickly totally removed and TOC, COD and BOD(5) final values of 123 mgC/L, 180 mgO(2)/L and 146 mgO(2)/L, respectively. Toxicity assessment by Vibrio fischeri light inhibition revealed that Fenton's process reduces the effluent ecological impact related with the decomposition of the toxic phenolic acids. Indeed, EC(50) changed from 32.2% dilution to no-dilution needed. The analysis of BOD(5)/COD ratio pointed out a high improvement of the treated wastewater biodegradability from 0.30 to 0.80 meaning that the application of Fenton's oxidation as a pre-treatment enables a further application of an efficient post-biological technology which was also confirmed by respirometry., (Copyright 2010 Elsevier B.V. All rights reserved.)

The development of a fingerprinting strategy capable to evaluate the "oxidation status" of white wines based on cyclic voltammetry is proposed here. It is known that the levels of specific antioxidants and redox mechanisms may be evaluated by cyclic voltammetry. This electrochemical technique was applied on two sets of samples. One group was composed of normal aged white wines and a second group obtained from a white wine forced aging protocol with different oxygen, SO(2), pH, and temperature regimens. A study of antioxidant additions, namely ascorbic acid, was also made in order to establish a statistical link between voltammogram fingerprints and chemical antioxidant substances. It was observed that the oxidation curve presented typical features, which enables sample discrimination according to age, oxygen consumption, and antioxidant additions. In fact, it was possible to place the results into four significant orthogonal directions, compressing 99.8% of nonrandom features. Attempts were made to make voltammogram fingerprinting a tool for monitoring oxidation management. For this purpose, a supervised multivariate control chart was developed using a control sample as reference. When white wines are plotted onto the chart, it is possible to monitor the oxidation status and to diagnose the effects of oxygen regimes and antioxidant activity. Finally, quantification of substances implicated in the oxidation process as reagents (antioxidants) and products (off-flavors) was tried using a supervised algorithmic the partial least square regression analysis. Good correlations (r > 0.93) were observed for ascorbic acid, Folin-Ciocalteu index, total SO(2), methional, and phenylacetaldehyde. These results show that cyclic voltammetry fingerprinting can be used to monitor and diagnose the effects of wine oxidation.

Walnut leaves from nine different cultivars (Arco, Franquette, Hartley, Lara, Marbot, Mayette, Meylannaise, Parisienne and Rego) were studied for their phenolic compounds. Samples were harvested along three consecutive years, at two different geographical locations, in order to evaluate if significant differences in the phenolics composition can be related with genetic, climatic or geographical factors. Nine compounds (3-caffeoylquinic, 3-p-coumaroylquinic and 4-p-coumaroylquinic acids, quercetin 3- galactoside, quercetin 3-arabinoside, quercetin 3-xyloside, quercetin 3-rhamnoside, a quercetin 3-pentoside derivative and a kaempferol 3-pentoside derivative) were quantified using an HPLC-DAD methodology. The qualitative profiles were identical for all samples, but differences were observed in terms of individual compounds' contents. Multivariate statistical analysis was carried out, showing that significant differences exist among production years, which can be related to climatic reasons.

The main purpose of this study was the characterisation of 'Serra da Lousã' heather honey by using novel statistical methodology, relevant principal component analysis, in order to assess the correlations between production year, locality and composition. Herein, we also report its chemical composition in terms of sugars, glycerol and ethanol, and physicochemical parameters. Sugars profiles from 'Serra da Lousã' heather and 'Terra Quente de Trás-os-Montes' lavender honeys were compared and allowed the discrimination: 'Serra da Lousã' honeys do not contain sucrose, generally exhibit lower contents of turanose, trehalose and maltose and higher contents of fructose and glucose. Different localities from 'Serra da Lousã' provided groups of samples with high and low glycerol contents. Glycerol and ethanol contents were revealed to be independent of the sugars profiles. These data and statistical models can be very useful in the comparison and detection of adulterations during the quality control analysis of 'Serra da Lousã' honey.

This paper presents a large amount of data on the composition of quince fruit with regard to phenolic compounds, organic acids, and free amino acids. Subsequently, principal component analysis (PCA) is carried out to characterize this fruit. The main purposes of this study were (i) the clarification of the interactions among three factors-quince fruit part, geographical origin of the fruits, and harvesting year-and the phenolic, organic acid, and free amino acid profiles; (ii) the classification of the possible differences; and (iii) the possible correlation among the contents of phenolics, organic acids, and free amino acids in quince fruit. With these aims, quince pulp and peel from nine geographical origins of Portugal, harvested in three consecutive years, for a total of 48 samples, were studied. PCA was performed to assess the relationship among the different components of quince fruit phenolics, organic acids, and free amino acids. Phenolics determination was the most interesting. The difference between pulp and peel phenolic profiles was more apparent during PCA. Two PCs accounted for 81.29% of the total variability, PC1 (74.14%) and PC2 (7.15%). PC1 described the difference between the contents of caffeoylquinic acids (3-O-, 4-O-, and 5-O-caffeoylquinic acids and 3,5-O-dicaffeoylquinic acid) and flavonoids (quercetin 3-galactoside, rutin, kaempferol glycoside, kaempferol 3-glucoside, kaempferol 3-rutinoside, quercetin glycosides acylated with p-coumaric acid, and kaempferol glycosides acylated with p-coumaric acid). PC2 related the content of 4-O-caffeoylquinic acid with the contents of 5-O-caffeoylquinic and 3,5-O-dicaffeoylquinic acids. PCA of phenolic compounds enables a clear distinction between the two parts of the fruit. The data presented herein may serve as a database for the detection of adulteration in quince derivatives.

Cupuaçu (Theobroma grandiflorum) is an Amazonian tropical fruit with a great economic potential. Pasteurization, by a hot-filling technique, was suggested for the preservation of this fruit pulp at room temperature. The process was implemented with local communities in Brazil. The process was modeled, and a computer program was written in Turbo Pascal. The relative importance among the pasteurization process variables (initial product temperature, heating rate, holding temperature and time, container volume and shape, cooling medium type and temperature) on the microbial target and quality was investigated, by performing simulations according to a screening factorial design. Afterward, simulations of the different processing conditions were carried out. The holding temperature (T(F)) and time (t(hold)) affected pasteurization value (P), and the container volume (V) influenced largely the quality parameters. The process was optimized for retail (1 L) and industrial (100 L) size containers, by maximizing volume average quality in terms of color lightness and sensory "fresh notes" and minimizing volume average total color difference and sensory "cooked notes". Equivalent processes were designed and simulated (P(91)( degrees )(C) = 4.6 min on Alicyclobacillus acidoterrestris spores) and final quality (color, flavor, and aroma attributes) was evaluated. Color was slightly affected by the pasteurization processes, and few differences were observed between the six equivalent treatments designed (T(F) between 80 and 97 degrees C). T(F) >/= 91 degrees C minimized "cooked notes" and maximized "fresh notes" of cupuaçu pulp aroma and flavor for 1 L container. Concerning the 100 L size, the "cooked notes" development can be minimized with T(F) >/= 91 degrees C, but overall the quality was greatly degraded as a result of the long cooling times. A more efficient method to speed up the cooling phase was recommended, especially for the industrial size of containers.