Degradation of the antibiotic amoxicillin by photo-Fenton process--chemical and toxicological assessment

The influence of iron species on amoxicillin (AMX) degradation, intermediate products generated and toxicity during the photo-Fenton process using a solar simulator were evaluated in this work. The AMX degradation was favored in the presence of the potassium ferrioxalate complex (FeOx) when compared to FeSO₄. Total oxidation of AMX in the presence of FeOx was obtained after 5 min, while 15 min were necessary using FeSO₄. The results obtained with Daphnia magna biossays showed that the toxicity decreased from 65 to 5% after 90 min of irradiation in the presence of FeSO₄. However, it increased again to a maximum of 100% after 150 min, what indicates the generation of more toxic intermediates than AMX, reaching 45% after 240 min. However, using FeOx, the inhibition of mobility varied between 100 and 70% during treatment, probably due to the presence of oxalate, which is toxic to the neonates. After 240 min, between 73 and 81% TOC removal was observed. Different pathways of AMX degradation were suggested including the opening of the four-membered β-lactamic ring and further oxidations of the methyl group to aldehyde and/or hydroxylation of the benzoic ring, generating other intermediates after bound cleavage between different atoms and further oxidation to carboxylates such acetate, oxalate and propionate, besides the generation of nitrate and ammonium.     

Microcystin-LR toxicity on dominant copepods Eurytemora affinis and Pseudodiaptomus forbesi of the upper San Francisco Estuary

This study investigates the toxicity and post-exposure effects of dissolved microcystin (MC-LR) on the dominant copepods of the upper San Francisco Estuary (SFE), where blooms of the toxic cyanobacteria Microcystis aeruginosa coincide with record low levels in the abundance of pelagic organisms including phytoplankton, zooplankton, and fish. The potential negative impact of Microcystis on the copepods Eurytemora affinis and Pseudodiaptomus forbesi has raised concern for further depletion of high quality fish food. Response of copepods to MC-LR (MC) was determined using a 48-h standard static renewal method for acute toxicity testing. Following exposure, a life table test was performed to quantify any post-exposure impacts on survival and reproduction. The 48-h LC-50 and LC-10 values for MC were 1.55 and 0.14 mg/L for E. affinis; and 0.52 and 0.21 mg/L for P. forbesi. Copepod populations recovered once dissolved MC was removed and cultures returned to optimal conditions, suggesting no post-exposure effects of MC on copepod populations. Dissolved microcystin above 0.14 mg/L proved likely to have chronic effects on the survival of copepods in the SFE. Since such high concentrations are unlikely, toxicity from dissolved microcystin is not a direct threat to zooplankton of the SFE, and other mechanisms such as dietary exposure to Microcystis constitute a more severe risk.     

Optimal aeration control in a nitrifying activated sludge process

An important tool to minimise energy consumption in activated sludge processes is to control the aeration system. Aeration is a costly process and the dissolved oxygen level will determine the efficiency of the operation as well as the treatment results. What aeration control should achieve is closely linked to how the effluent criteria are defined. This paper explores how the aeration process should be controlled to meet the effluent discharge limits in an energy efficient manner in countries where the effluent nitrogen criterion is defined as average values over long time frames, such as months or years. Simulations have been performed using a simplified Benchmark Simulation Model No. 1 to investigate the effect of different levels of suppressing the variations of the effluent ammonium concentration. Optimisation is performed where the manipulated variable for aeration (the oxygen transfer coefficient, K_La) is minimised with the constraint that the average daily flow-proportional ammonium concentration in the effluent should reach a desired level. The optimisation results are compared with constant dissolved oxygen concentrations and supervisory ammonium control with different controller settings. The results demonstrate and explain how and why energy consumption can be optimised by tolerating the ammonium concentration to vary around a given average value. In these simulations, the optimal oxygen peak-to-peak amplitude range between 0.7 and 1.8 mg/l depending on the influent variation and ammonium level in the effluent. These variations can be achieved with a slow ammonium feedback controller. The air flow requirements can be reduced by 1-4% compared to constant dissolved oxygen set-points. Optimal control of aeration requires up to 14% less energy than needed for fast feedback control of effluent ammonium.     

Photo-Fenton-like treatment of BPA: Effect of UV light source and water matrix on toxicity and transformation products

UV-A (near-UV), UV-C (short-UV) and visible-light assisted Fenton-like treatment of Bisphenol A (BPA) was investigated in pure water and raw freshwater samples spiked with BPA. Treatment performances were evaluated in terms of BPA degradation, dissolved organic carbon (DOC) removal and H₂O₂ consumption rates. Complete BPA degradation accompanied with significant DOC removal was achieved for all studied processes. Increasing the initial solution pH only exhibited a negative effect on treatment efficiencies when bicarbonate alkalinity was used for pH adjustment, whereas the raw freshwater matrix and irradiation type also influenced oxidation rates appreciably. Acute toxicity analysis employing Vibrio fischeri revealed that the inhibitory effect of BPA decreased significantly during the course of Photo-Fenton-like treatment. Several transformation products could be identified via HPLC and GC–MS analyses including hydroxylated phenolic compounds (hydroquinone; 2-methoxy, 1-4-benzenediol; 4-isopropenylphenol; 4′-hydroxy-acetophenone; 1-(4-cyclohexylphenyl) ethanone; 4-isopropylenecatechol; 4-4′-dihydroxybenzophenone; 4-ethyl,1,3-benzenediol), as well as the ring opening products hexanoic acid methyl ester, fumaric, succinic and oxalic acids. A reaction pathway featuring hydroxylation, dimerization and ring opening steps is proposed.     

Nitrate removal, communities of denitrifiers and adverse effects in different carbon substrates for use in denitrification beds

Denitrification beds are containers filled with wood by-products that serve as a carbon and energy source to denitrifiers, which reduce nitrate (NO₃⁻) from point source discharges into non-reactive dinitrogen (N₂) gas. This study investigates a range of alternative carbon sources and determines rates, mechanisms and factors controlling NO₃⁻ removal, denitrifying bacterial community, and the adverse effects of these substrates. Experimental barrels (0.2 m³) filled with either maize cobs, wheat straw, green waste, sawdust, pine woodchips or eucalyptus woodchips were incubated at 16.8 °C or 27.1 °C (outlet temperature), and received NO₃⁻ enriched water (14.38 mg N L⁻¹ and 17.15 mg N L⁻¹). After 2.5 years of incubation measurements were made of NO₃⁻-N removal rates, in vitro denitrification rates (DR), factors limiting denitrification (carbon and nitrate availability, dissolved oxygen, temperature, pH, and concentrations of NO₃⁻, nitrite and ammonia), copy number of nitrite reductase (nirS and nirK) and nitrous oxide reductase (nosZ) genes, and greenhouse gas production (dissolved nitrous oxide (N₂O) and methane), and carbon (TOC) loss. Microbial denitrification was the main mechanism for NO₃⁻-N removal. Nitrate-N removal rates ranged from 1.3 (pine woodchips) to 6.2 g N m⁻³ d⁻¹ (maize cobs), and were predominantly limited by C availability and temperature (Q₁₀ = 1.2) when NO₃⁻-N outlet concentrations remained above 1 mg L⁻¹. The NO₃⁻-N removal rate did not depend directly on substrate type, but on the quantity of microbially available carbon, which differed between carbon sources. The abundance of denitrifying genes (nirS, nirK and nosZ) was similar in replicate barrels under cold incubation, but varied substantially under warm incubation, and between substrates. Warm incubation enhanced growth of nirS containing bacteria and bacteria that lacked the nosZ gene, potentially explaining the greater N₂O emission in warmer environments. Maize cob substrate had the highest NO₃⁻-N removal rate, but adverse effects include TOC release, dissolved N₂O release and substantial carbon consumption by non-denitrifiers. Woodchips removed less than half of NO₃⁻ removed by maize cobs, but provided ideal conditions for denitrifying bacteria, and adverse effects were not observed. Therefore we recommend the combination of maize cobs and woodchips to enhance NO₃⁻ removal while minimizing adverse effects in denitrification beds.     

Effect of dissolved oxygen on the photodecomposition of monochloramine and dichloramine in aqueous solution by UV irradiation at 253.7 nm

The effect of dissolved oxygen on the photodecomposition of monochloramine (7.5 < pH < 10) and dichloramine (pH = 3.7 ± 0.2) at 253.7 nm has been investigated. The kinetic study shows that the rate of photodecomposition of monochloramine is about two times faster in the absence of oxygen than in the presence of oxygen, is not significantly affected by pH and by the presence of hydroxyl radical scavengers (hydrogenocarbonate ion and tert-butanol). The apparent quantum yields of photodecomposition of monochloramine at 253.7 nm ([NH₂Cl]₀ ≈ 1.5-2 mM, ?_{253.7 nm} = 371 M⁻¹ cm⁻¹) were equal to 0.28 ± 0.03 and 0.54 ± 0.03 mol E⁻¹ in oxygenated-saturated and in oxygen-free solutions, respectively. The photodecomposition rates or the apparent quantum yields of photodecomposition of dichloramine ([NHCl₂]₀ ≈ 1.5-2 mM, pH = 3.7 ± 0.2) in oxygen-free and in oxygen-saturated solutions were quite identical (Φ = 0.82 ± 0.08 mol E⁻¹; ?_{253.7 nm} = 126 M⁻¹ cm⁻¹). Under O₂ saturation, UV irradiation of NH₂Cl leads to the formation of nitrite (≈0.37 mol/mol of NH₂Cl decomposed), nitrate (≈0.073 mol/mol) and does not form ammonia (<0.01 mol/mol). In oxygen-free solutions, monochloramine decomposes to form ammonia (≈0.37 mol/mol). Photodecomposition of dichloramine did not lead to significant amounts of nitrite and nitrate in the presence and in the absence of oxygen. The nitrogen mass balances also indicate the formation of other nitrogen species (probably N₂ and/or N₂O) during the photodecomposition of monochloramine and dichloramine by UV irradiation at 253.7 nm.     

Degradation of the emerging contaminant ibuprofen in water by photo-Fenton

In this study the degradation of the worldwide Non-Steroidal Anti-Inflammatory Drug (NSAID) ibuprofen (IBP) by photo-Fenton reaction by use of solar artificial irradiation was carried out. Non-photocatalytic experiments (complex formation, photolysis and UV/Vis-H₂O₂ oxidation) were executed to evaluate the isolated effects and additional differentiated degradation pathways of IBP. The solar photolysis cleavage of H₂O₂ generates hydroxylated-IBP byproducts without mineralization. Fenton reaction, however promotes hydroxylation with a 10% contamination in form of a mineralization. In contrast photo-Fenton in addition promotes the decarboxylation of IBP and its total depletion is observed. In absence of H₂O₂ a decrease of IBP was observed in the Fe(II)/UV-Vis process due to the complex formation between iron and the IBP-carboxylic moiety. The degradation pathway can be described as an interconnected and successive principal decarboxylation and hydroxylation steps. TOC depletion of 40% was observed in photo-Fenton degradation. The iron-IBP binding was the key-point of the decarboxylation pathway. Both decarboxylation and hydroxylation mechanisms, as individual or parallel process are responsible for IBP removal in Fenton and photo-Fenton systems. An increase in the biodegradability of the final effluent after photo-Fenton treatment was observed. Final BOD₅ of 25 mg L⁻¹ was reached in contrast to the initial BOD₅ shown by the untreated IBP solution (BOD₅ < 1 mg L⁻¹). The increase in the biodegradability of the photo-Fenton degradation byproducts opens the possibility for a complete remediation with a final post-biological treatment.     

Photo-Fenton degradation of the herbicide tebuthiuron under solar irradiation: Iron complexation and initial intermediates

The complexation of iron ions with the herbicide tebuthiuron (TBH), during a solar photo-Fenton process, was investigated using cyclic voltammetry with a glassy carbon electrode. An oxidation peak was observed at +0.64 V after addition of Fe(NO₃)₃ to TBH solution, indicating the formation of a Fe-TBH complex, which was not observed in the presence of ferrioxalate or citrate complexes. This complexation hinders photoreduction of Fe(III), and consequently TBH degradation. The main degradation route, in the presence or absence of citric acid (in the latter case with Fe(NO₃)₃ only), is initiated by the hydroxylation of a terminal methyl group of the urea, indicating an identical degradation mechanism. Hydroxylation of the central methyl of urea, and of the tert-butyl group, was also observed after extended irradiation periods in the presence of citric acid, but was not observed in the presence of Fe(NO₃)₃, due to a slower degradation rate in the absence of the citrate complex. No intermediate, generated from opening of the thiadiazole ring, was identified under the various different conditions.     

Early-stage anaerobic zone formation by organic eluate from wood in soil

When separated soil (SS) generated from the Great East Japan Earthquake, which contains woodchips and others (WC), is utilized as ground material, microorganisms decompose the organic carbon in WC, and oxygen is consumed in the process. This reaction results in forming an anaerobic zone and generating methane gas. To effectively utilize SS as ground material, it is necessary to prevent anaerobic zone formation to ensure safety. This study clarified the relationship between WC content and the concentration of leached organic carbon (TOC) and the relationship between TOC concentration in the eluate and the oxygen consumption rate were clarified. We obtained the relationship between WC content and the extent of anaerobic zone formation from the results,. The anaerobic zone is formed below the oxygen penetration depth (L_O2). L_O2 rapidly decreases as the WC weight ratio increases from 0 to 1 w%, and L_O2 is almost constant, i.e., around 1 to 2 m above 1 w% WC weight ratio. An increase in WC weight ratio does not significantly decrease L_O2 determined by the aerobic decomposition of the solution. From the above, contamination with WC should be limited to 1 w% or less to prevent the formation of an anaerobic zone. If SS has WC above 1 w%, it is required to put a ventilating layer such as crushed stone every few meters or the other countermeasures when SS is utilized as ground material.     

Electrochemical oxidation of trace organic contaminants in reverse osmosis concentrate using RuO2/IrO2-coated titanium anodes

During membrane treatment of secondary effluent from wastewater treatment plants, a reverse osmosis concentrate (ROC) containing trace organic contaminants is generated. As the latter are of concern, effective and economic treatment methods are required. Here, we investigated electrochemical oxidation of ROC using Ti/Ru_0.7Ir_0.3O₂ electrodes, focussing on the removal of dissolved organic carbon (DOC), specific ultra-violet absorbance at 254 nm (SUVA₂₅₄), and 28 pharmaceuticals and pesticides frequently encountered in secondary treated effluents. The experiments were conducted in a continuously fed reactor at current densities (J) ranging from 1 to 250 A m⁻² anode, and a batch reactor at J = 250 A m⁻². Higher mineralization efficiency was observed during batch oxidation (e.g. 25.1 ± 2.7% DOC removal vs 0% removal in the continuous reactor after applying specific electrical charge, Q = 437.0 A h m⁻³ ROC), indicating that DOC removal is depending on indirect oxidation by electrogenerated oxidants that accumulate in the bulk liquid. An initial increase and subsequent slow decrease in SUVA₂₅₄ during batch mode suggests the introduction of auxochrome substituents (e.g. -Cl, NH₂Cl, -Br, and -OH) into the aromatic compounds. Contrarily, in the continuous reactor ring-cleaving oxidation products were generated, and SUVA₂₅₄ removal correlated with applied charge. Furthermore, 20 of the target pharmaceuticals and pesticides completely disappeared in both the continuous and batch experiments when applying J ≥ 150 A m⁻² (i.e. Q ≥ 461.5 A h m⁻³) and 437.0 A h m⁻³ (J = 250 A m⁻²), respectively. Compounds that were more persistent during continuous oxidation were characterized by the presence of electrophilic groups on the aromatic ring (e.g. triclopyr) or by the absence of stronger nucleophilic substituents (e.g. ibuprofen). These pollutants were oxidized when applying higher specific electrical charge in batch mode (i.e. 1.45 kA h m⁻³ ROC). However, baseline toxicity as determined by Vibrio fischeri bioluminescence inhibition tests (Microtox) was increasing with higher applied charge during batch and continuous oxidation, indicating the formation of toxic oxidation products, possibly chlorinated and brominated organic compounds.     

The influence of dissolved and surface-bound humic acid on the toxicity of TiO₂ nanoparticles to Chlorella sp

NOM is likely to coat TiO₂ nanoparticles (nano-TiO₂) discharged into the aquatic environment and influence the nanotoxicity to aquatic organisms, which however has not been well investigated. This study explored the influence of nanoparticle surface-bound humic acid (HA, as a model NOM) as well as dissolved HA on the toxicity of nano-TiO₂ to Chlorella sp., with a specific focus on adhesion of the nanoparticles to the algae. Results showed that nano-TiO₂ and the dissolved HA could inhibit the algal growth with an IC₅₀ of 4.9 and 8.4 mg L⁻¹, respectively, while both dissolved and nanoparticle surface-bound HA could significantly alleviate the algal toxicity of nano-TiO₂. IC₅₀ of nano-TiO₂ increased to 18 mg L⁻¹ in the presence of 5 mg L⁻¹ of the dissolved HA and to 48 mg L⁻¹ as the result of surface-saturation by HA. Co-precipitation experiment and transmission electron microscopy observation revealed that both dissolved and nanoparticle surface-bound HA prevented the adhesion of nano-TiO₂ to the algal cells due to the increased electrosteric repulsion. The generation of intracellular reactive oxygen species (ROS) was significantly limited by the dissolved and nanoparticle surface-bound HA. The prevention of adhesion and inhibition of ROS generation could account for the HA-mitigated nanotoxicity.     

Transformation mechanism of benzophenone-4 in free chlorine promoted chlorination disinfection

The UV-filter BP-4 (2-hydroxy-4-methoxybenzophenone-5-sulfonic acid) has been frequently observed in the environment, showing high potentials to invade drinking water, swimming water, or wastewater reclamation treatment systems. With the help of high performance liquid chromatography-high resolution mass spectrometry and nuclear magnetic resonance spectroscopy, 10 new products from free chlorine-promoted BP-4 disinfection have been disclosed and their possible transformation routes have been investigated. The first route is chlorine substitution of BP-4 and its transformation products, forming mono-, di-, and tri-chlorinated BP-4 analogs. The second is Baeyer–Villiger-Type oxidation, converting diphenyl ketone to phenyl ester derivatives. The third is ester hydrolysis, generating corresponding phenolic and benzoic products. The fourth is decarboxylation, replacing the carboxyl group by chloride in the benzoic-type intermediate. The fifth is desulfonation, degrading the sulfonic group through an alternative chlorine substitution on the benzene ring. Orthogonal experiments have been established to investigate the species transformed from BP-4 at different pH values and free available chlorine (FAC) dosages. The reaction pathways are strongly dependent on pH conditions, while an excessive amount of FAC eliminates BP-4 to the smaller molecules. The initial transformation of BP-4 in chlorination system follows pseudo-first-order kinetics, and its half-lives ranged from 7.48 s to 1.26 × 10² s. More importantly, we have observed that the FAC-treated BP-4 aqueous solution might increase the genotoxic potentials due to the generation of chlorinated disinfection by-products.     

Dynamics of sulphur compounds in horizontal sub-surface flow laboratory-scale constructed wetlands treating artificial sewage

The knowledge regarding the dynamics of sulphur compounds inside constructed wetlands is still insufficient. Experiments in planted (Juncus effusus) and unplanted horizontal sub-surface-flow laboratory-scale constructed wetlands fed with artificial wastewater were carried out to evaluate the sulphate reduction, the composition and dynamics of generated sulphur compounds, as well as the influence of carbon load and plants on processes of sulphur transformation.In planted and unplanted wetlands, the addition of organic carbon (TOC of about 120 mg L⁻¹) immediately affected the transformation of up to 90% of the incoming sulphate (150 mg L⁻¹), directing it mainly towards elemental sulphur (30%) and sulphide (8%). During this experimental period, nearly 52% of the transformed sulphate-sulphur was calculated to be immobilized inside the planted wetland and 66% inside the unplanted one.In subsequent experiments, the deficiency of organic carbon inside the planted wetlands favoured the decrease of elemental sulphur in the pore water coupled to retransformation of depot-sulphur to dissolved sulphate. Nearly 90% of the deposited and reduced sulphur was found to be reoxidized. In principle, the results indicate a substantial improvement of this reoxidation of sulphur by oxygen released by the helophytes. Surplus of organic carbon promotes the ongoing sulphate reduction and the stability of deposed and dissolved reduced sulphur compounds.In contrast, inside the unplanted control wetland, a relative stability of the formed sulphur depots and the generated amount of dissolved sulphur compounds including elemental sulphur could be observed independently of the different loading conditions.     

Silver-modified mesoporous TiO2 photocatalyst for water purification

Mesoporous anatase (TiO₂) was modified with silver (Ag) nanoparticles using a photoreduction method. Performance of the resulting TiO₂-Ag nanocomposites for water purification was evaluated using degradation of Rhodamine B (RhB) and disinfection of Escherichia coli (E. coli) under ultraviolet (UV) irradiation. The composites with different Ag loadings were characterized using physical adsorption of nitrogen, X-ray diffraction, X-ray photoelectron spectroscopy and UV-Visible diffuse reflectance spectroscopic techniques. The results showed that metallic Ag nanoparticles were firmly immobilized on the TiO₂ surface, which improved electron-hole separation by forming the Schottky barrier at the TiO₂-Ag interface. Photocatalytic degradation of RhB and inactivation of E. coli effectively occurred in an analogical trend. The deposited Ag slightly decreased adsorption of target pollutants, but greatly increased adsorption of molecular oxygen with the latter enhancing production of reactive oxygen species (ROSs) with concomitant increase in contaminant photodegradation. The optimal Ag loadings for RhB degradation and E. coli disinfection were 0.25 wt% and 2.0 wt%, respectively. The composite photocatalysts were stable and could be used repeatedly under UV irradiation.     

In-situ identification of iron electrocoagulation speciation and application for natural organic matter (NOM) removal

In this work, iron speciation in electrocoagulation (EC) was studied to determine the impact of operating parameters on natural organic matter (NOM) removal from natural water. Two electrochemical EC parameters, current density (i) and charge loading rate (CLR), were investigated. Variation of these parameters led to a near unity current efficiency (φ = 0.957 ± 0.03), at any combination of i in a range of 1–25 mA/cm² and CLR in a range of 12–300 C/L/min. Higher i and CLR led to a higher bulk pH and limited the amount of dissolved oxygen (DO) reduced at the cathode surface due to mass transfer limitations. A low i (1 mA/cm²) and intermediate CLR (60 C/L/min) resulted in low bulk DO (<2.5 mg/L), where green rust (GR) was identified by in-situ Raman spectroscopy as the primary crystalline electrochemical product. Longer electrolysis times at higher i led to magnetite (Fe₃O₄) formation. Both higher (300 C/L/min) and lower (12 C/L/min) CLR values led to increased DO and/or increased pH, with lepidocrocite (γ-FeOOH) as the only crystalline species observed. The NOM removal of the three identified species was compared, with conditions leading to GR formation showing the greatest dissolved organic carbon removal, and highest removal of the low apparent molecular weight (<550 Da) chromophoric NOM fraction, determined by high performance size exclusion chromatography.     

Depth-resolved abundance and diversity of arsenite-oxidizing bacteria in the groundwater of Beimen,a blackfoot disease endemic area of southwestern Taiwan

The role of arsenite oxidizers in natural attenuation of arsenic pollution necessitates studies on their abundance and diversity in arsenic-contaminated aquifers. In this study, most probable number-polymerase chain reaction (MPN-PCR) and denaturing gradient gel electrophoresis (DGGE) was applied to monitor depth-wise abundance and diversity of aerobic arsenite oxidizers in arsenic-enriched groundwater of Beimen, southwestern Taiwan. The results revealed that the abundance of arsenite oxidizers ranged from 0.04 to 0.22, and the lowest ratio was observed in the most arsenic-enriched and comparatively more reduced groundwater (depth 200 m) of Beimen 1. The highest ratio was observed in the less arsenic-enriched and less reduced groundwater (depth 60 m) of Beimen 2B. DGGE profiles showed a shift in diversity of arsenite oxidizers, consisting of members of the Betaproteobacteria (61%), Alphaproteobacteria (28%) and Gammaproteobacteria (11%), depending on mainly arsenic concentration and redox level in groundwater. Groundwater with the lowest arsenic and highest dissolved oxygen at Beimen 2B harbored 78% of the arsenite oxidizers communities, while groundwater with the highest arsenic and lowest dissolved oxygen at Beimen 1 and Beimen–Jinhu harbored 17 and 22% of arsenite oxidizers communities, respectively. Pseudomonas sp. was found only in groundwater containing high arsenic at Beimen 1 and Beimen–Jinhu, while arsenite oxidizers belonging to Alpha- and Betaproteobacteria were dominated in groundwater containing low arsenic.     

Photocatalytic degradation of propachlor in aqueous TiO2 suspensions. Determination of the reaction pathway and identification of intermediate products by various analytical methods

The light-induced degradation of propachlor (2-chloro-N-isopropylacetanilide) under simulated solar irradiation has been investigated in aqueous solutions containing TiO2 suspensions as photocatalysts. The study focuses on the identification of possible intermediate products and the determination of inorganic ions formed during the process, using several powerful analytical techniques such as gas chromatography mass-spectrometry (GC-MS) and ion chromatography. The primary degradation of propachlor has been a fast process with a half-live time of 2.3 min and followed pseudo-first-order kinetics according to the Langmuir-Hinshelwood model. The mineralization of the organic carbon to CO2 after 240 min of irradiation was found to be < 63%. The corresponding stoichiometric transformation of organic chlorine into chloride ion was reached in 30 min, whereas oxidation of nitrogen to nitrate ions took place at delayed irradiation times. Various aromatic intermediates have been identified by GC/MS techniques during the treatment, which were involved into three tentative degradation routes. One, was based on the dechlorination through positive holes or solvated electrons to form the hydroxy or aliphatic derivative. The second route consists of the rupture of amide bond or the N-C bond via nitrogen ionization by positive holes and through the ring hydroxylation, respectively. Finally, the third possible degradation route was based on hydrogen abstraction by the hydroxyl radicals or positive holes, followed either by the addition of oxygen to the alkyl radical or the decomposition of the peroxyl radical formed. From the analytical data, a possible multi-step degradation scheme was proposed. This work points to the necessity of extended knowledge of the successive steps in a solar-assisted detoxification process.