Fenton Conditions Research Articles

Two-stage treatment of pulp bleaching wastewater by Fenton and biological processes to remove recalcitrant pollutants

In this work, Fenton and aerobic biological processes were successfully coupled to treat pulp bleaching wastewater. The goal was to find a treatment solution to simultaneously maximise the removal of recalcitrant pollutants (adsorbable organic halides – AOX) and organic load (COD) from that wastewater. To that end, two treatment setups were studied: (i) aerobic biological process (activated sludge) followed by Fenton; and (ii) Fenton followed by aerobic biological process. Treatment by biological process followed by Fenton allowed for an overall removal of AOX and COD of 89.5 % and 82.5 %, respectively, at the optimised Fenton conditions determined by Response Surface Methodology: 489 mM H2O2, 9.3 mM Fe2+, and 49.2 min of treatment. Under the inverse treatment setup, an overall removal of 89.6 % AOX and 71.9 % COD was attained. Moreover, it was proven that the microbiological activity was not greatly affected by neither the initial organic load, nor the existence of Fenton chemicals and transformation products in the wastewater composition. Although the treatment sequence Biological → Fenton presented maximum overall performance, operating costs associated with this solution were over 2-fold higher than the inverse sequence, owing to the higher demand of chemicals.

Broad Spectral Response FeOOH/BiO2-x Photocatalyst with Efficient Charge Transfer for Enhanced Photo-Fenton Synergistic Catalytic Activity.

In this work, to promote the separation of photogenerated carriers, prevent the catalyst from photo-corrosion, and improve the photo-Fenton synergistic degradation of organic pollutants, the coating structure of FeOOH/BiO2-x rich in oxygen vacancies was successfully synthesized by a facile and environmentally friendly two-step process of hydrothermal and chemical deposition. Through a series of degradation activity tests of synthesized materials under different conditions, it was found that FeOOH/BiO2-x demonstrated outstanding organic pollutant degradation activity under visible and near-infrared light when hydrogen peroxide was added. After 90 min of reaction under photo-Fenton conditions, the degradation rate of Methylene Blue by FeOOH/BiO2-x was 87.4%, significantly higher than the degradation efficiency under photocatalysis (60.3%) and Fenton (49.0%) conditions. The apparent rate constants of FeOOH/BiO2-x under photo-Fenton conditions were 2.33 times and 3.32 times higher than photocatalysis and Fenton catalysis, respectively. The amorphous FeOOH was tightly coated on the layered BiO2-x, which significantly increased the specific surface area and the number of active sites of the composites, and facilitated the improvement of the separation efficiency of the photogenerated carriers and the prevention of photo-corrosion of BiO2-x. The analysis of the mechanism of photo-Fenton synergistic degradation clarified that ·OH, h+, and ·O2- are the main active substances involved in the degradation of pollutants. The optimal degradation conditions were the addition of the FeOOH/BiO2-x composite catalyst loaded with 20% Fe at a concentration of 0.5 g/L, the addition of hydrogen peroxide at a concentration of 8 mM, and an initial pH of 4. This outstanding catalytic system offers a fresh approach to the creation and processing of iron-based photo-Fenton catalysts by quickly and efficiently degrading various organic contaminants.

Proton-Conducting Membranes from Polyphenylenes Containing Armstrong's Acid.

This study demonstrates the use of 1,5-naphthalenedisulfonic acid as a suitable building block for the efficient and economic preparation of alternating sulfonated polyphenylenes with high ion-exchange capacity (IEC) via Suzuki polycondensation. Key to large molar masses is the use of an all-meta-terphenyl comonomer instead of m-phenyl, the latter giving low molar masses and brittle materials. A protection/deprotection strategy for base-stable neopentyl sulfonates is successfully implemented to improve the solubility and molar mass of the polymers. Solution-based deprotection of polyphenylene neopentyl sulfonates at 150 °C in dimethylacetamide eliminates isopentylene quantitatively, resulting in membranes with high IEC (2.93 mequiv/g) and high proton conductivity (σ = 138 mS/cm). Water solubility of these copolymers with high IEC requires thermal cross-linking to prevent their dissolution under operating conditions. By balancing the temperature and time of the cross-linking process, water uptake can be restricted to 50 wt %, retaining an IEC of 2.33 mequiv/g and a conductivity of 85 mS/cm. Chemical stability is addressed by treatment of the membranes under Fenton's conditions and by considering barrier heights for desulfonation using density functional theory (DFT) calculations. The DFT results suggest that 1,5-disulfonated naphthalenes are at least as stable as sulfonated polyphenylenes against desulfonation.

Neutral pH Fenton and photo-Fenton activity of Mo-doped iron-pyrite particles.

Low H2O2 utilization efficiency for hydroxyl radical generation, acidic pH, and recyclability are critical limitations of heterogeneous Fenton and photo-Fenton catalysts. The present research shows that the optimum Mo doping of FeS2 particles can largely alleviate these catalysis constraints. A solvothermal protocol was followed to prepare polyvinyl pyrrolidone (PVP) stabilized FeS2 and Mo-doped FeS2 particles. XRD observations showed that Mo doping increases the lattice parameters of FeS2. The band gap of the Mo-doped FeS2 particles decreased to 1.58 eV from the 2.24 eV value exhibited by pure FeS2 particles. Structural and electronic structure DFT calculations support these results. The Fenton and photo-Fenton p-nitrophenol (PNP) degradation at neutral pH on PVP-stabilized Mo-doped FeS2 and FeS2 particles were examined. The photo-Fenton results were substantially better than under Fenton conditions. The best PNP degradation photo-Fenton turnover frequency (TOF) recorded was 254.50 μmol g-1 min-1 on the PVP stabilized 4% Mo-doped FeS2 sample. The Mo-doped FeS2 catalysts were stable under photo-Fenton recycling, and the H2O2 (1.66 mM) required for these reactions was significantly lower than most reports (30-6000 mM). Given the economic importance of the latter in Fenton/photo-Fenton reactions, H2O2 normalized turnover frequency (13.85 and 153.31 mg-1 min-1 L for Fenton and photo-Fenton) values were used to evaluate catalytic activities.

An extra-chelator-free fenton process assisted by electrocatalytic-induced in-situ pollutant carboxylation for target refractory organic efficient treatment in chemical-industrial wastewater

For traditional Fenton processes, the quenching behavior of radical contenders (e.g., most aliphatic hydrocarbons) on hydroxyl radicals (·OH) usually hinders the removal of target refractory pollutants (aromatic/heterocyclic hydrocarbons) in chemical industrial wastewater, leading to excess energy consumption. Herein, we proposed an electrocatalytic-assisted chelation-Fenton (EACF) process, with no extra-chelator addition, to significantly enhance target refractory pollutant (pyrazole as a representative) removal under high ·OH contender (glyoxal) levels. Experiments and theoretical calculations proved that superoxide radical (·O2−) and anodic direct electron transfer (DET) effectively converted the strong ·OH-quenching substance (glyoxal) to a weak radical competitor (oxalate) during the electrocatalytic oxidation process, promoting Fe2+ chelation and therefore increasing radical utilization for pyrazole degradation (reached maximum of ∼43-fold value upon traditional Fenton), which appeared more obviously in neutral/alkaline Fenton conditions. For actual pharmaceutical tailwater treatment, the EACF achieved 2-folds higher oriented-oxidation capability and ∼78% lower operation cost per pyrazole removal than the traditional Fenton process, demonstrating promising potential for future practical applications.

Insights into the effects of Fenton oxidation on PAH removal and indigenous bacteria in aged subsurface soil

Combined chemical oxidation and bioremediation is a promising method of treating polycyclic aromatic hydrocarbon (PAH) contaminated soil, wherein indigenous soil bacteria play a critical role in the subsequent biodegradation of PAHs after the depletion of the oxidant. In this study, different Fenton conditions were applied by varying either the oxidation mode (conventional Fenton (CF), Fenton-like (LF), modified Fenton (MF), and graded modified Fenton (GMF)) or the H2O2 dosage (0%, 3%, 6%, and 10% (v/v)) to treat PAH contaminated soil. The results revealed that when equal dosages of H2O2 are applied, PAHs are significantly removed following oxidation treatment, and the removal percentages obeyed the following sequence: CF > GMF > MF > LF. In addition, higher dosages of H2O2 improved the PAH removal from soil treated with the same oxidation mode. The ranges of total PAHs removal efficiencies in the soil added 3%, 6%, and 10% of H2O2 (v/v) were 18.04%∼59.48%, 31.88%∼71.83%, and 47.56%∼78.16%, respectively. The PAH removal efficiency decreased with increasing ring numbers for the same oxidation treatment. However, the negative influences on soil bacterial abundance, community composition, and function were observed after Fenton treatment. After Fenton oxidation, the bacterial abundance in the soil received 3%, 6%, and 10% of H2O2 (v/v) decreased 1.96–2.69, 2.44–3.22, and 3.09–3.42 orders of magnitude compared to the untreated soil. The soil bacterial abundance tended to be impacted by the oxidation mode and H2O2 dosage simultaneously. While the main factor influencing the soil bacterial community composition was the H2O2 dosages. The results of this study showed that different oxidation mode and H2O2 dosage exhibited different effects on PAHs removal and soil bacteria (including abundance, community composition, and function), and there was a trade-off between the removal of PAHs and the adverse impact on soil bacteria.

Luminescent pro-nitroxide lanthanide complexes for the detection of reactive oxygen species.

The DOTA-based ligand H3L (5) appended with a pro-nitroxide moiety has been synthesized. The europium and ytterbium complexes 5Ln show metal-centred luminescence. They react with ROS in aqueous media to give a transient iminonitroxide and a stable nitronylnitroxide radical authenticated by EPR, with change in luminescence.

Reactivity of 4-thiothymidine with Fenton reagent investigated by UV-visible spectroscopy and electrospray ionization mass spectrometry.

The reactivity of the sulfur-containing nucleoside 4-thio-(2'-deoxy)-thymidine usually abbreviated as 4-thio-thymidine, (S4 -TdR) under Fenton conditions, ie, in the presence of H2 O2 and catalytic amounts of Fe(II), was investigated by UV-vis spectroscopy and electrospray ionization single and tandem mass spectrometry (ESI-MS and MS/MS). S4 -TdR hydroxylated on the S atom was found to be a key reaction intermediate, ultimately leading to (2'-deoxy)-thymidine usually abbreviated as thymidine, (TdR) as the main reaction product. This finding was in accordance with the outcome of the reaction between S4 -TdR and H2 O2 , previously investigated in our laboratory. On the other hand, the additional presence of •OH radicals, induced by the Fe(II)/H2 O2 combination, led to the increased generation of another interesting S4 -TdR product, already observed after its reaction with H2 O2 alone, ie, the covalent dimer including a SS bridge between two S4 -TdR molecules. More importantly, multihydroxylated derivatives of S4 -TdR and TdR were detected as peculiar products obtained under Fenton conditions. Among them, a product bearing an OH group both on the methyl group linked to the thymine ring and on the C5 atom of the ring was found to prevail. The results obtained during this study, integrated by those found previously in our laboratory, indicate 4-thiothymidine as a promising molecular probe for the recognition, through a careful characterization of its reaction products, of the prevailing species among reactive oxygen species (ROS) corresponding to singlet-state oxygen, hydrogen peroxide, and hydroxylic radical.

Supercritical water oxidation of p-aminonaphthalenesulfonic acid and enhancement by Fenton agent

ABSTRACT The introduction of Fe2+ into supercritical water oxidation (SCWO) and the formation of Fenton reagent with oxidant H2O2 form a new environment, namely, supercritical Fenton oxidation (SCFO) environment. p-Aminonaphthalenesulfonic acid was selected as the typical organic pollutant to explore the effects of temperature, oxidant multiple, reaction time and Fenton conditions on the TOC removal rate. SCFO showed the superiority in the degradation of organic matter compared with the SCWO. The oxidative degradation kinetics of p-aminonaphthalenesulfonic acid in SCFO environment was further explored. Under SCFO condition, the oxidative degradation of p-aminonaphthalene sulfonic acid was consistent with first-order reaction kinetics. The results showed that the activation energy Ea and pre exponential factor k 0 were 39.937 kJ·mol−1 and 1.94 × 104 s−1 respectively.

Fenton treatment of bio-treated fermentation-based pharmaceutical wastewater: removal and conversion of organic pollutants as well as estimation of operational costs.

The Fenton process is used as a tertiary treatment to remove organic pollutants from the effluent of bio-treated pharmaceutical wastewater (EBPW). The optimal and most appropriate Fenton conditions were determined by an orthogonal array test and single-factor experiments. The removal of chemical oxygen demand (COD) was influenced by the following factors in a descending order: H2O2/Fe(II) molar ratio > H2O2 dosage > reaction time. Under the most appropriate Fenton conditions (H2O2/Fe(II) molar ratio of 1:1, H2O2 dosage of 120mgL-1 and reaction time of 10min), the COD and dissolved organic carbon (DOC) were removed with efficiencies of 62 and 53%, respectively, which met the national discharge standard (GB 21903-2008) for the Lake Tai Basin, China. However, the Fenton treatment was inadequate for removal of N compounds, and the removal of organic nitrogen led to an increment in N-NH3 from 3.28 to 19.71mgL-1. Proteins and polysaccharides were completely removed, and humic acids (HAs) were partly removed with an efficiency of 55%. Three-dimensional excitation/emission matrix spectra (3DEEMs) indicated complete removal of fulvic acid-like substances and 90% reduction in the florescence intensity of humic acid-like substances. Organic pollutants with molecular weights (MW) > 10kDa were completely removed, MW 5-10kDa were degraded into smaller MW ones, and some low molecular weight acids (MW 0.1-1kDa) were mineralized during the Fenton process. Some species, including pharmaceutical intermediates and solvents were detected by gas chromatography-mass spectrometry (GC-MS). The operational costs of the Fenton's treatment were estimated to be 0.58yuanRMB/m3 EBPW based on reagent usage and iron sludge treatment and disposal.

Comparison of Fenton, ultraviolet–Fenton and ultrasonic–Fenton processes on organics and colour removal from pre-treated natural gas produced water

Produced water (PW) from natural gas field, characterized with high organic contents, has brought high environmental concerns world widely. Fenton and enhanced Fenton technologies were considered as the potential methods to degrade the organic contaminates in the PW, but with very limited data or reference. Here, we examined the optimum conditions of Fenton on organics and colour removal from natural gas PW after coagulation pre-treatment. Simultaneously, the optimal Fenton process integrated with ultraviolet (UV) and ultrasonic (US) irradiation were applied to enhance pollutants removal efficiencies. The optimal Fenton conditions were found at 60 min with molar ratios of 6:1 and 25:1 for H2O2/COD and H2O2/Fe2+, respectively and the initial pH of 3. Among these the three treatment processes, chemical oxygen demand (COD), total organic carbon, 5-day biological oxygen demand (BOD5), and colour removal efficiencies were highest during UV–Fenton (82, 73, 68, and 95%,) followed by US–Fenton (79, 70, 66, and 95%) and Fenton treatment (70, 58, 51, and 92%), respectively. High biodegradability (BOD5/COD) was also observed after UV–Fenton process (0.76) than the others (both 0.73). The current study showed a satisfactory carbon and colour removal efficiencies from PW using different Fenton processes; however, there still is a need for final polishing such as biological treatment or low cost constructed wetland before discharge. This study can be a good reference for engineering application PW treatment.

Determination of Cod and Color Reduction of Stabilized Landfill Leachate by Fenton Process

The Fenton process on landfill leachate was done in a batch reactor. The application of Fenton treatment technology for landfill leachate treatment greatly depends on the optimum Fenton operating conditions. The present study investigated the chemical oxygen demand (COD) and color removal efficiency of a non-biodegradable leachate by Fenton process. Determining optimum Fenton conditions requires multiple experiments using variable reaction parameters (pH, temperature, and H2O2 and Fe2+ doses).The treatment showed that the leachate organics can be broke down by the use of Fenton?s reagent. The result showed that with increasing H2O2 dosage, H2O2/Fe2+ ratio and decreasing the pH and contact time, the COD and color removal increased. The laboratory result determined that the best functional situation to catch the goals _ (i.e., BOD5/COD =0.1) resulted; pH=3, Contact time=30 minutes, H2O2 concentration= 40000 mgL-1 and the favorable H2O2/Fe2+ ratio = 10.

Theoretical and experimental formation of low chlorinated dibenzo-p-dioxins and dibenzofurans in the Fenton oxidation of chlorophenol solutions

The formation of chlorinated and non-chlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) has been experimentally investigated after the Fenton oxidation of 2-chlorophenol (2-CP, 15.56 mM) aqueous solutions by assessing the influence of iron concentration (0.09–2.88 mM), hydrogen peroxide dose (40.44–202.20 mM), temperature (20–70 °C) and chloride concentration (0–56.35 mM). The presence of chloride in the medium together with room temperature and substoichiometric Fenton conditions (40.44 mM H2O2) led to an increase in total PCDD/Fs concentration from less than 1 ng L−1 to 2 μg L−1. Results showed a dominance of the dichlorinated species (DCDD/Fs) in the homologue profile of total PCDD/Fs reaching values up to 1.5 μg L−1. Furthermore, the products distribution exhibited a gradual decrease in the homologue concentration as the chlorination degree increased from di-to octachloro-substituted positions. Considering the characteristics of the reaction medium, the experimental results, and the information gathered in bibliography with regard to the generation of active radicals from 2-chlorophenol, a mechanism describing the formation of low chlorinated PCDD/Fs in a Fenton oxidizing aqueous system has been proposed.

Photo–Fenton reaction in the presence of morphologically controlled hematite as iron source

Abstract Hematite particles with controlled size and shape (cubic, spherical and ovoidal, with size range from hundreds nm to μm) were produced by modulating the conditions of synthesis and were characterized by different techniques (XRD spectroscopy, scanning electron microscopy, BET analysis, dynamic light scattering, UV–vis spectroscopy). The photoactivity of the synthesized hematite particles was tested towards the degradation of phenol under photo–Fenton conditions, obtaining optimal results in the pH range 3–4. Although the smaller particles have a larger contact interface between the solid and the solution, no obvious relationship was found between size and photoactivity. A possible explanation is that the smallest particles tested showed an important radiation scattering, which would interfere with radiation absorption and, therefore, with photoactivity. In contrast, the most photoactive samples were those showing the highest concentrations of leached iron. This issue would imply that photoactivity may be related to partial dissolution of hematite with formation of Fe(II) and of photo-active Fe(III) species, which activate the classic photo–Fenton process. Anyway, leached Fe was limited to the μg L −1 range that is safely far from the mg L −1 limits for wastewater.

Visible Light-Accelerated Depolymerisation of Starch Under Fenton Conditions and Preparation of Calcium Sequestering Compounds

Oxidation of starch under Fenton conditions leads to a mixture of acids having Ca sequestering properties. The efficiency of the process increases under visible light irradiation; this is mainly due to the improvement of the depolymerization of the substrate. Whatever the experimental conditions, that is Fenton or photo-Fenton, the oxidation products promote the oxidation step.

Fenton treatment of landfill leachate under different COD loading factors

The application of Fenton treatment technology for treatment of landfill leachate greatly depends on the optimum Fenton operating conditions for a specific leachate. Determining optimum Fenton conditions requires multiple experiments using variable reaction parameters (pH, temperature, and H2O2 and Fe2+ doses) and previous researches show a wide range of optimal operating conditions. In this study, the applicability of the dimensionless loading factor (LCOD), which is defined as the initial COD (COD0) of leachate with respect to available O2 for oxidation, was examined to derive optimum Fenton oxidant dose using reduced set of experiments. The Fenton experiments were conducted using leachates with three different COD0 concentrations, 1092, 546, and 273mgL−1, LCOD in the range of 0.25–1.0, and H2O2/Fe2+ 1.8 (w/w). The experimental data were analyzed to determine the correlation between the LCOD factor and selected feasibility parameters, amongst which were: (i) the COD removal kinetics, (ii) the total COD removal, (iii) the usability of H2O2 with respect to COD removal, (iv) leachate biodegradability, and (v) treatment cost incurred by chemical usage. The experimental COD removal with respect to the amount of O2 supplied by H2O2 was compared with respect to the optimum COD removal efficiency by the equation: ηFPoptimum=0.733LCOD-0.182 as developed by Singh and Tang (2013) and a LCOD of 0.75 was determined to be the optimum LCOD for leachate treatment.

Oxidative degradation of acid doped polybenzimidazole membranes and fuel cell durability in the presence of ferrous ions

Phosphoric acid doped polybenzimidazole membranes have been explored as proton exchange membranes for high temperature polymer electrolyte membrane fuel cells. Long-term durability of the membrane is of critical concern and has been evaluated by accelerated degradation tests under Fenton conditions. In this study effects of phosphoric acid and ferrous ions were investigated by measurements of the weight loss, intrinsic viscosity and size exclusion chromatography (SEC) of the polymer membranes. Ferrous ions resulted in, as expected, catalytic formation of peroxide radicals and hence the accelerated polymer degradation in terms of weight loss and molecular weight decrease. The presence of phosphoric acid as an inevitable dopant of the membranes, on the other hand, significantly impeded the membrane degradation by means of metal ion complexing, decreased pH, and acid–base interactions with the amino groups of the polymer. Fuel cell durability tests with contaminations of ferrous ions did show considerable performance degradation, however, primarily due to the catalyst deterioration rather than the membrane degradation.

Superoxide Reaction with Tyrosyl Radicals Generates para-Hydroperoxy and para-Hydroxy Derivatives of Tyrosine

Tyrosine-derived hydroperoxides are formed in peptides and proteins exposed to enzymatic or cellular sources of superoxide and oxidizing species as a result of the nearly diffusion-limited reaction between tyrosyl radical and superoxide. However, the structure of these products, which informs their reactivity in biology, has not been unequivocally established. We report here the complete characterization of the products formed in the addition of superoxide, generated from xanthine oxidase, to several peptide-derived tyrosyl radicals, formed from horseradish peroxidase. RP-HPLC, LC-MS, and NMR experiments indicate that the primary stable products of superoxide addition to tyrosyl radical are para-hydroperoxide derivatives (para relative to the position of the OH in tyrosine) that can be reduced to the corresponding para-alcohol. In the case of glycyl-tyrosine, a stable 3-(1-hydroperoxy-4-oxocyclohexa-2,5-dien-1-yl)-L-alanine was formed. In tyrosyl-glycine and Leu-enkephalin, which have N-terminal tyrosines, bicyclic indolic para-hydroperoxide derivatives were formed ((2S,3aR,7aR)-3a-hydroperoxy-6-oxo-2,3,3a,6,7,7a-hexahydro-1H-indole-2-carboxylic acid) by the conjugate addition of the free amine to the cyclohexadienone. It was also found that significant amounts of the para-OH derivative were generated from the hydroxyl radical, formed on exposure of tyrosine-containing peptides to Fenton conditions. The para-OOH and para-OH derivatives are much more reactive than other tyrosine oxidation products and may play important roles in physiology and disease.

Mineralization of Catechol by Fenton and Photo‐Fenton Processes

AbstractCatechol is one of the most abundant phenolic components of olive mill wastewaters. In this article, the mineralization of this compound in synthetic aqueous solutions by the Fenton and photo‐Fenton processes is studied. It has been found that for 1.44 mM catechol, the total organic carbon of solutions is reduced about 94.4% at best after 60 min of Fenton treatment at optimized conditions of pH 3.0, 0.2 mM Fe2+, 7.09 mM H2O2, and 25°C. A faster and overall mineralization is attained by applying photo‐Fenton with UVA irradiation. o‐Benzoquinone, 1,2,3‐trihydroxybenzene and 1,2,4‐trihydroxybenzene were identified by GC–MS as primary quinonic and polyhydroxylated derivatives. Small amounts of generated carboxylic acids like muconic, maleic, malonic, acetic, oxalic, and formic acids were detected by ion‐exclusion chromatography. The Fe(III) complexes of these acids persist in the medium under Fenton conditions, while their photolysis by UVA light and that of other by‐products account for by the faster degradation and total mineralization achieved in the photo‐Fenton process. A reaction sequence for catechol mineralization by Fenton and photo‐Fenton involving all intermediates detected is proposed.

Characterization of oxidation products from 1-palmitoyl-2-linoleoyl-sn-glycerophosphatidylcholine in aqueous solutions and their reactions with cysteine, histidine and lysine residues

This report focuses on studies of lipid peroxidation products reactivity towards the side chains of cysteine, histidine, and lysine residues in structurally unordered peptides. Thus we have analyzed linoleic acid peroxidation products (LaPP) obtained by incubating 1-palmitoyl-2-linoleoyl-sn-glycerophosphatidylcholine (PLPC) overnight with or without H2O2 in the presence or absence of CuCl. In total, 55 different LaPP were identified with 26 containing reactive carbonyl groups. The strongest oxidation conditions (H2O2 and Cu(I), i.e. a Fenton-like reagent) yielded 51 LaPP, whereas air oxidation produced only 12 LaPP. Independent of the oxidation conditions, around half of all LaPP were short-chain (oxidative cleavage) and the others long-chain (oxygen addition) PLPC oxidation products. The stronger oxidation conditions increased the number of LaPP, but also oxidized the added peptide Ac-PAAPAAPAPAEXTPV-OH (X=Cys, His or Lys) very quickly, especially under Fenton conditions. Thus, PLPC was oxidized by milder conditions (air or Cu(I)), incubated with the peptide and the peptide modifications were then analyzed by nano-RPC-ESI-Orbitrap-MS. Ten LaPP-derived peptide modifications were identified at lysine, whereas nine products were identified for cysteine and only three for histidine. Three high molecular weight LaPP still esterified to the GPC backbone were detected on Lys-containing peptide. Furthermore, three LaPP-derived mass shifts were obtained at cysteine, which have not previously been reported.