Ordinal Regression with Fenton-Wilkinson Order Statistics: A Case Study of an Orienteering Race

In sports, individuals and teams are typically interested in final rankings. Final results, such as times or distances, dictate these rankings, also known as places. Places can be further associated with ordered random variables, commonly referred to as order statistics. In this work, we introduce a simple, yet accurate order statistical ordinal regression function that predicts relay race places with changeover-times. We call this function the Fenton-Wilkinson Order Statistics model. This model is built on the following educated assumption: individual leg-times follow log-normal distributions. Moreover, our key idea is to utilize Fenton-Wilkinson approximations of changeover-times alongside an estimator for the total number of teams as in the notorious German tank problem. This original place regression function is sigmoidal and thus correctly predicts the existence of a small number of elite teams that significantly outperform the rest of the teams. Our model also describes how place increases linearly with changeover-time at the inflection point of the log-normal distribution function. With real-world data from Jukola 2019, a massive orienteering relay race, the model is shown to be highly accurate even when the size of the training set is only 5% of the whole data set. Numerical results also show that our model exhibits smaller place prediction root-mean-square-errors than linear regression, mord regression and Gaussian process regression.

Evaluation of Produced Water Treatment Using Advanced Oxidation Processes and Sodium Ferrate(VI)

Oil and gas exploration is an essential activity for modern society, although the supply of its global demand has caused enough damage to the environment, mainly due to produced water generation, which is an effluent associated with the oil and gas produced during oil extraction. It is the aim of this study to evaluate the treatment of produced water, in order to reduce its oils and greases content (OG), by using flotation as a pre-treatment, combined with oxidation for the remaining organic load degradation. Thus, there has been tested Advanced Oxidation Process (AOP) using both Fenton and photo-Fenton reactions, as well as a chemical oxidation treatment using sodium ferrate(VI), Na2[FeO4], as a strong oxidant. All the studies were carried out using real samples of produced water from petroleum industry. The oxidation process using ferrate(VI) ion was studied based on factorial experimental designs. The factorial design was used in order to study how the variables pH, temperature and concentration of Na2[FeO4] influences the O&G levels. For the treatment using ferrate(VI) ion, the results showed that the best operating point is obtained when the temperature is 28 °C, pH 3, and a 2000 mg.L-1 solution of Na2[FeO4] is used. This experiment has achieved a final O&G level of 4.7 mg.L-1, which means 94% percentage removal efficiency of oils and greases. Comparing Fenton and photo-Fenton processes, it was observed that the Fenton reaction did not provide good reduction of O&G (around 20% only). On the other hand, a degradation of approximately 80.5% of oil and grease was obtained after a period of seven hours of treatment using photo-Fenton process, which indicates that the best process combination has occurred between the flotation and the photo-Fenton reaction using solar radiation, with an overall removal efficiency of O&G of approximately 89%.

Sulfur Removal of Hydrocarbon Fuels Using Oxidative Desulfurization Enhanced by Fenton Process

A comprehensive development towards the production of ultra-clean fuels as a feed stoke is getting to raise due to the increasing use of diesel fuels and global air pollution. Production of environmental-friendly fuels can be achievable by some limited single methods and most integrated ones. Oxidative desulfurization (ODS) presents vast ranges of technologies possessing suitable characteristics with regard to the Fenton process. Using toluene as a model fuel feed with dibenzothiophene (DBT) as a sulfur compound under various operating conditions is the attempt of this study. The results showed that this oxidative process followed a pseudo-first order kinetics. Removal efficiency of 77.43% is attained under reaction time of 40 minutes with (Fe+2/H2O2) molar ratio of 0.05 in acidic pH environment. In this research, temperature of 50 °C represented the most influential role in proceeding the reaction.

Preparation of Heterogeneous Ferrite Catalysts and Their Application for Fenton-Like Oxidation of Radioactive Organic Wastewater

Fenton oxidation technology is the general strategy for the treatment of organic compounds-contained wastewater. However, a considerable amount of ferric sludge was produced during the Fenton process as secondary wastes, which were needed to be further removed from the effluent and treated. In this study, heterogeneous catalysts based on ferrite oxide (Cu-Fe-Ce-O) were synthesized and characterized, and their application for Fenton-like oxidation of simulated and actual radioactive organic wastewater was investigated. The results of TOC decomposition efficiency around 54% ~ 99% were obtained when the catalyst loading, H2O2 loading, pH, temperature, and reaction time were controlled. In this case, no secondary wastes formed and the given catalysts were able to be separated by magnetic devices and reused again.

Role of Organic Wastewater Constituents in Iron Redox Cycling for Ferric Sludge Reuse in the Fenton-Based Treatment

The practical application of the Fenton-based treatment method for organic compounds-contaminated water purification is limited mainly because of the large amount of ferric sludge formed during the treatment, where ferrous iron (Fe(II)) is used as the activator of the hydrogen peroxide oxidation processes. Reuse of ferric sludge collected from clarifiers to substitute Fe(II) salts allows reducing the total cost of Fenton-type treatment technologies and minimizing the accumulation of hazardous ferric waste. Dissolution of ferric iron (Fe(III)) from the sludge to liquid phase at acidic pH and autocatalytic transformation of Fe(III) to Fe(II) by phenolic compounds (tannic acid, lignin, phenol, catechol, pyrogallol and hydroquinone) added or present as water/wastewater constituents were found to be essentially involved in the Fenton-based oxidation mechanism. Observed enhanced formation of highly reactive species, hydroxyl radicals, resulted in a substantial organic contaminant degradation increase. Sludge reuse at acidic pH and in the presence of ferric iron reductants is a novel strategy in the Fenton-based treatment application for organic compounds-contaminated water purification.

Flocculation on the Treatment of Olive Oil Mill Wastewater: Pretreatment

Currently, continuous two-phase decanter process used for olive oil production is the more internationally widespread. The wastewaters generated from this industry (OMW) are a real environmental problem because of its high organic load. Among proposed treatments for these wastewaters, advanced oxidation technologies (Fenton, ozone, photoFenton, etc.) are the most favourable. The direct application of these processes is somewhat expensive. Therefore, the application of a previous stage based on a flocculation-sedimentation operation is of high importance. In this research five commercial flocculants (three cationic, and two anionic) have been used to achieve the separation of phases (liquid clarifiedsludge). For each flocculant, different concentrations (0-1000 mg/L) have been studied. In these experiments, sludge volume formed and the final water quality were determined. The final removal percentages of total phenols (11.3-25.1%), COD (5.6-20.4%), total carbon (2.3-26.5%), total organic carbon (1.50-23.8%), total nitrogen (1.45-24.8%), and turbidity (27.9-61.4%) were determined. The variation on electric conductivity reduction percentage (1-8%) was also determined. Finally, the best flocculants with highest removal percentages have been determined (QG2001 and Flocudex CS49).

Treatment of Cutting Oily-Wastewater by Sono Fenton Process: Experimental Approach and Combined Process

Conventional coagulation, advance oxidation process (AOPs), and the combined process were evaluated and compared for its suitability to treat the stabilized cutting-oil wastewater. The 90% efficiency was obtained from the coagulation at Al2(SO4)3 dosage of 150 mg/L and pH 7. On the other hands, efficiencies of AOPs for 30 minutes oxidation time were 10% for acoustic oxidation, 12% for acoustic oxidation with hydrogen peroxide, 76% for Fenton, and 92% sono-Fenton processes. The highest efficiency for effective oil removal of AOPs required large amount of chemical. Therefore, AOPs were studied as a post-treatment after conventional separation process. The efficiency was considerable as the effluent COD can pass the standard required for industrial wastewater discharge with less chemical and energy consumption.  

Ultrasonic Intensification of the Chemical Degradation of Methyl Violet: An Experimental Study

The sonochemical decolorization and degradation of azo dye Methyl violet using Fenton-s reagent in the presence of a high-frequency acoustic field has been investigated. Dyeing and textile effluents are the major sources of azo dyes, and are most troublesome among industrial wastewaters, causing imbalance in the eco-system. The effect of various operating conditions (initial concentration of dye, liquid-phase temperature, ultrasonic power and frequency and process time) on sonochemical degradation was investigated. Conversion was found to increase with increase in initial concentration, temperature, power level and frequency. Both horntype and tank-type sonicators were used, at various power levels (250W, 400W and 500W) for frequencies ranging from 20 kHz - 1000 kHz. A 'Process Intensification' parameter PI, was defined to quantify the enhancement of the degradation reaction by ultrasound when compared to control (i.e., without ultrasound). The present work clearly demonstrates that a high-frequency ultrasonic bath can be used to achieve higher process throughput and energy efficiency at a larger scale of operation.

Removal of Phenylurea Herbicides from Waters by using Chemical Oxidation Treatments

Four phenylurea herbicides (isoproturon, chlortoluron, diuron and linuron) were dissolved in different water matrices in order to study their chemical degradation by using UV radiation, ozone and some advanced oxidation processes (UV/H2O2, O3/H2O2, Fenton reagent and the photo- Fenton system). The waters used were: ultra-pure water, a commercial mineral water, a groundwater and a surface water taken from a reservoir. Elimination levels were established for each herbicide and for several global quality parameters, and a kinetic study was performed in order to determine basic kinetic parameters of each reaction between the target phenylureas and these oxidizing systems.

A Comparison Study of the Removal of Selected Pharmaceuticals in Waters by Chemical Oxidation Treatments

The degradation of selected pharmaceuticals in some water matrices was studied by using several chemical treatments. The pharmaceuticals selected were the beta-blocker metoprolol, the nonsteroidal anti-inflammatory naproxen, the antibiotic amoxicillin, and the analgesic phenacetin; and their degradations were conducted by using UV radiation alone, ozone, Fenton-s reagent, Fenton-like system, photo-Fenton system, and combinations of UV radiation and ozone with H2O2, TiO2, Fe(II), and Fe(III). The water matrices, in addition to ultra-pure water, were a reservoir water, a groundwater, and two secondary effluents from two municipal WWTP. The results reveal that the presence of any second oxidant enhanced the oxidation rates, with the systems UV/TiO2 and O3/TiO2 providing the highest degradation rates. It is also observed in most of the investigated oxidation systems that the degradation rate followed the sequence: amoxicillin > naproxen > metoprolol > phenacetin. Lower rates were obtained with the pharmaceuticals dissolved in natural waters and secondary effluents due to the organic matter present which consume some amounts of the oxidant agents.

Chelate Enhanced Modified Fenton Treatment for Polycyclic Aromatic Hydrocarbons Contaminated Soils

This work focuses on the remediation of polycyclic aromatic hydrocarbons (PAHs)-contaminated soil via Fenton treatment coupled with novel chelating agent (CA). The feasibility of chelated modified Fenton (MF) treatment to promote PAH oxidation in artificially contaminated soils was investigated in laboratory scale batch experiments at natural pH. The effects of adding inorganic and organic CA are discussed. Experiments using different iron catalyst to CA ratios were conducted, resulting in hydrogen peroxide: soil: iron: CA weight ratios that varied from 0.049: 1: 0.072: 0.008 to 0.049: 1: 0.072: 0.067. The results revealed that (1) inorganic CA could provide much higher PAH removal efficiency and (2) most of the proposed CAs were more efficient than commonly utilised CAs even at mild ratio. This work highlights the potential of novel chelating agents in maintaining a suitable environment throughout the Fenton treatment, particularly in soils with high buffer capacity.

Solar Photo-Fenton Induced Degradation of Combined Chlorpyrifos, Cypermethrin and Chlorothalonil Pesticides in Aqueous Solution

The feasibility of employing solar radiation for enhanced Fenton process in degradation of combined chlorpyrifos, cypermethrin and chlorothalonil pesticides was examined. The effect of various operating conditions of the process on biodegradability improvement and mineralization of the pesticides were also evaluated. The optimum operating conditions for treatment of aqueous solution containing 100, 50 and 250 mg L-1 chlorpyrifos cypermethrin and chlorothalonil, respectively were observed to be H2O2/COD molar ratio 2, H2O2/Fe2+ molar ratio 25 and pH 3. Under the optimum operating conditions, complete degradation of the pesticides occurred in 1 min. Biodegradability (BOD5/COD) increased from zero to 0.36 in 60 min, and COD and TOC removal were 74.19 and 58.32%, respectively in 60 min. Due to mineralization of organic carbon, decrease in ammonia-nitrogen from 22 to 4.3 mg L-1 and increase in nitrate from 0.7 to 18.1 mg L-1 in 60 min were recorded. The study indicated that solar photo-Fenton process can be used for pretreatment of chlorpyrifos, cypermethrin and chlorothalonil pesticides in aqueous solution for further biological treatment.

The Mechanistic and Oxidative Study of Methomyl and Parathion Degradation by Fenton Process

The purpose of this study is to investigate the chemical degradation of the organophosphorus pesticide of parathion and carbamate insecticide of methomyl in the aqueous phase through Fenton process. With the employment of batch Fenton process, the degradation of the two selected pesticides at different pH, initial concentration, humic acid concentration, and Fenton reagent dosages was explored. The Fenton process was found effective to degrade parathion and methomyl. The optimal dosage of Fenton reagents (i.e., molar concentration ratio of H2O2 to Fe2+) at pH 7 for parathion degradation was equal to 3, which resulted in 50% removal of parathion. Similarly, the optimal dosage for methomyl degradation was 1, resulting in 80% removal of methomyl. This study also found that the presence of humic substances has enhanced pesticide degradation by Fenton process significantly. The mass spectroscopy results showed that the hydroxyl free radical may attack the single bonds with least energy of investigated pesticides to form smaller molecules which is more easily to degrade either through physio-chemical or bilolgical processes.

Photo-Fenton Treatment of 1,3-dichloro-2- Propanol Aqueous Solutions Using UV Radiation and H2O2 – A Kinetic Study

The photochemical and photo-Fenton oxidation of 1,3-dichloro-2-propanol was performed in a batch reactor, at room temperature, using UV radiation, H2O2 as oxidant, and Fenton-s reagent. The effect of the oxidative agent-s initial concentration was investigated as well as the effect of the initial concentration of Fe(II) by following the target compound degradation, the total organic carbon removal and the chloride ion production. Also, from the kinetic analysis conducted and proposed reaction scheme it was deduced that the addition of Fe(II) significantly increases the production and the further oxidation of the chlorinated intermediates.

Optimisation of Polycyclic AromaticHydrocarbon Removal from Contaminated Soilusing Modified Fenton Treatment

The performance of modified Fenton (MF) treatment to promote PAH oxidation in artificially contaminated soil was investigated in packed soil column with a hydrogen peroxide (H2O2) delivery system simulating in situ injection. Soil samples were spiked with phenanthrene (low molecular weight PAH) and fluoranthene (high molecular weight PAH) to an initial concentration of 500 mg/kg dried soil each. The effectiveness of process parameters H2O2/soil, iron/soil, chelating agent/soil weight ratios and reaction time were studied using a 24 three level factorial design experiments. Statistically significant quadratic models were developed using Response Surface Methodology (RSM) for degrading PAHs from the soil samples. Optimum operating condition was achieved at mild range of H2O2/soil, iron/soil and chelating agent/soil weight ratios, indicating cost efficient method for treating highly contaminated lands.

Remediation of Petroleum Hydrocarbon-contaminated Soil Slurry by Fenton Oxidation

Theobjective of this study was to evaluate the optimal treatment condition of Fenton oxidation process to removal contaminant in soil slurry contaminated by petroleum hydrocarbons. This research studied somefactors that affect the removal efficiency of petroleum hydrocarbons in soil slurry including molar ratio of hydrogen peroxide (H2O2) to ferrous ion(Fe2+), pH condition and reaction time.The resultsdemonstrated that the optimum condition was that the molar ratio of H2O2:Fe3+ was 200:1,the pHwas 4.0and the rate of reaction was increasing rapidly from starting point to 7th hour and destruction kinetic rate (k) was 0.24 h-1. Approximately 96% of petroleum hydrocarbon was observed(initialtotal petroleum hydrocarbon (TPH) concentration = 70±7gkg-1)

Comparison of Different Advanced Oxidation Processes for Degrading 4-Chlorophenol

The removal efficiency of 4-chlorophenol with different advanced oxidation processes have been studied. Oxidation experiments were carried out using two 4-chlorophenol concentrations: 100 mg L-1 and 250 mg L-1 and UV generated from a KrCl excilamp with (molar ratio H2O2: 4-chlorophenol = 25:1) and without H2O2, and, with Fenton process (molar ratio H2O2:4- chlorophenol of 25:1 and Fe2+ concentration of 5 mg L-1). The results show that there is no significant difference in the 4- chlorophenol conversion when using one of the three assayed methods. However, significant concentrations of the photoproductos still remained in the media when the chosen treatment involves UV without hydrogen peroxide. Fenton process removed all the intermediate photoproducts except for the hydroquinone and the 1,2,4-trihydroxybenzene. In the case of UV and hydrogen peroxide all the intermediate photoproducts are removed. Microbial bioassays were carried out utilising the naturally luminescent bacterium Vibrio fischeri and a genetically modified Pseudomonas putida isolated from a waste treatment plant receiving phenolic waste. The results using V. fischeri show that with samples after degradation, only the UV treatment showed toxicity (IC50 =38) whereas with H2O2 and Fenton reactions the samples exhibited no toxicity after treatment in the range of concentrations studied. Using the Pseudomonas putida biosensor no toxicity could be detected for all the samples following treatment due to the higher tolerance of the organism to phenol concentrations encountered.

Removal of Pharmaceutical Compounds by a Sequential Treatment of Ozonation Followed by Fenton Process: Influence of the Water Matrix

A sequential treatment of ozonation followed by a Fenton or photo-Fenton process, using black light lamps (365 nm) in this latter case, has been applied to remove a mixture of pharmaceutical compounds and the generated by-products both in ultrapure and secondary treated wastewater. The scientifictechnological innovation of this study stems from the in situ generation of hydrogen peroxide from the direct ozonation of pharmaceuticals, and can later be used in the application of Fenton and photo-Fenton processes. The compounds selected as models were sulfamethoxazol and acetaminophen. It should be remarked that the use of a second process is necessary as a result of the low mineralization yield reached by the exclusive application of ozone. Therefore, the influence of the water matrix has been studied in terms of hydrogen peroxide concentration, individual compound concentration and total organic carbon removed. Moreover, the concentration of different iron species in solution has been measured.

Fenton’s Oxidation as Post-Treatment of a Mature Municipal Landfill Leachate

Mature landfill leachates contain some macromolecular organic substances that are resistant to biological degradation. Recently, Fenton-s oxidation has been investigated for chemical treatment or pre-treatment of mature landfill leachates. The aim of this study was to reduce the recalcitrant organic load still remaining after the complete treatment of a mature landfill leachate by Fenton-s oxidation post-treatment. The effect of various parameters such as H2O2 to Fe2+ molar ratio, dosage of Fe2+ reagent, initial pH, reaction time and initial chemical oxygen demand (COD) strength, that have an important role on the oxidation, was analysed. A molar ratio H2O2/Fe2+ = 3, a Fe2+ dosage of 4 mmol·L-1, pH 3, and a reaction time of 40 min were found to achieve better oxidation performances. At these favorable conditions, COD removal efficiency was 60.9% and 31.1% for initial COD of 93 and 743 mg·L-1 respectively (diluted and non diluted leachate). Fenton-s oxidation also presented good results for color removal. In spite of being extremely difficult to treat this leachate, the above results seem rather encouraging on the application of Fenton-s oxidation.

Catalytic Decomposition of Potassium Monopersulfate. The Kinetics

Potassium monopersulfate has been decomposed in aqueous solution in the presence of Co(II). The process has been simulated by means of a mechanism based on elementary reactions. Rate constants have been taken from literature reports or, alternatively, assimilated to analogous reactions occurring in Fenton's chemistry. Several operating conditions have been successfully applied.