Degradation of propyl paraben by activated persulfate using iron-containing magnetic carbon xerogels: investigation of water matrix and process synergy effects

An advanced oxidation process comprising an iron-containing magnetic carbon xerogel (CX/Fe) and persulfate was tested for the degradation of propyl paraben (PP), a contaminant of emerging concern, in various water matrices. Moreover, the effect of 20 kHz ultrasound or light irradiation on process performance was evaluated. The pseudo-first order degradation rate of PP was found to increase with increasing SPS concentration (25–500 mg/L) and decreasing PP concentration (1690–420 μg/L) and solution pH (9–3). Furthermore, the effect of water matrix on kinetics was detrimental depending on the complexity (i.e., wastewater, river water, bottled water) and the concentration of matrix constituents (i.e., humic acid, chloride, bicarbonate). The simultaneous use of CX/Fe and ultrasound as persulfate activators resulted in a synergistic effect, with the level of synergy (between 35 and 50%) depending on the water matrix. Conversely, coupling CX/Fe with simulated solar or UVA irradiation resulted in a cumulative effect in experiments performed in ultrapure water.     

Extent of sonochemical degradation and change of toxicity of a pharmaceutical precursor (triphenylphosphine oxide) in water as a function of treatment conditions

The degradation of triphenylphosphine oxide (TPPO) in water, a toxic compound typically found in effluents from the pharmaceutical industry, by means of ultrasonic irradiation at 20 kHz has been investigated with emphasis on the effect of various parameters on conversion and acute toxicity. Experiments were carried out at liquid volumes of 50 and 80 ml, electric power outputs of 125, 187.5 and 250 W, initial TPPO concentrations of 10, 100 and 350 mg/L and temperatures of 5, 20, 35, 50 and 70 degrees C. TPPO conversion was found to increase with increasing power output and decreasing initial concentration and temperature. Measurements of dissolved total carbon showed that liquid-phase degradation by-products were more stable to ultrasonic irradiation than TPPO. Addition of t-butanol as a radical scavenger at a concentration of 1000 mg/L nearly completely suppressed TPPO degradation. Conversely, addition of radical promoters (Fe(2+) ions or H(2)O(2)) had a positive effect on degradation. Acute toxicity to marine bacteria vibrio fischeri was measured before and after ultrasonic irradiation. At the conditions employed in this study, irradiated TPPO samples were always more toxic than TPPO itself with toxicity levels being a function of treatment conditions.     

Sonochemical reduction of the antioxidant activity of olive mill wastewater

The use of ultrasonic irradiation to reduce the antioxidant activity of olive oil mill wastewaters (OMWs) originating from two-phase and three-phase decanters was examined. Sonication of diluted OMW samples was conducted at ultrasonic frequencies of 24 and 80 kHz, an applied power varying between 75 and 150 W, and liquid bulk temperatures varying between 25 and 60 degrees C. At the conditions in question, the reduction in antioxidant activity was found to increase with decreasing temperature and increasing power and frequency. Addition of NaCl in the samples also appeared to enhance reduction. Antioxidant activity of OMW samples was assessed using the recently developed Co(II)/ethylenediaminetetraacetic acid (EDTA)-induced luminol chemiluminescence analytical protocol, while the total phenolic load was measured according to the Folin-Ciocalteu method.     

Treatment of municipal landfill leachate by catalytic wet air oxidation: Assessment of the role of operating parameters by factorial design

The wet air oxidation (WAO) of municipal landfill leachate catalyzed by cupric ions and promoted by hydrogen peroxide was investigated. The effect of operating conditions such as WAO treatment time (15-30 min), temperature (160-200 °C), Cu²⁺ concentration (250-750 mg L⁻¹) and H₂O₂ concentration (0-1500 mg L⁻¹) on chemical oxygen demand (COD) removal was investigated by factorial design considering a two-stage, sequential process comprising the heating-up of the reactor and the actual WAO. The leachate, at an initial COD of 4920 mg L⁻¹, was acidified to pH 3 leading to 31% COD decrease presumably due to the coagulation/precipitation of colloidal and other organic matter. During the 45 min long heating-up period of the WAO reactor under an inert atmosphere, COD removal values up to 35% (based on the initial COD value) were recorded as a result of the catalytic decomposition of H₂O₂ to reactive hydroxyl radicals. WAO at 2.5 MPa oxygen partial pressure advanced treatment further; for example, 22 min of oxidation at 200 °C, 250 mg L⁻¹ Cu²⁺ and 0-1500 mg L⁻¹ H₂O₂ resulted in an overall (i.e. including acidification and heating-up) COD reduction of 78%. Amongst the operating variables in question, temperature had the strongest influence on both the heating-up and WAO stages, while H₂O₂ concentration strongly affected the former and reaction time the latter. Nonetheless, the effects of temperature and H₂O₂ concentration were found to depend on the concentration levels of catalyst as suggested by the significance of their 3rd order interaction term.     

Removal of residual pharmaceuticals from aqueous systems by advanced oxidation processes

Over the past few years, pharmaceuticals are considered as an emerging environmental problem due to their continuous input and persistence to the aquatic ecosystem even at low concentrations. Advanced oxidation processes (AOPs) are technologies based on the intermediacy of hydroxyl and other radicals to oxidize recalcitrant, toxic and non-biodegradable compounds to various by-products and eventually to inert end-products. The environmental applications of AOPs are numerous, including water and wastewater treatment (i.e. removal of organic and inorganic pollutants and pathogens), air pollution abatement and soil remediation. AOPs are applied for the abatement of pollution caused by the presence of residual pharmaceuticals in waters for the last decade. In this light, this paper reviews and assesses the effectiveness of various AOPs for pharmaceutical removal from aqueous systems.     

Coupling digestion in a pilot-scale UASB reactor and electrochemical oxidation over BDD anode to treat diluted cheese whey

The efficiency of the anaerobic treatment of cheese whey (CW) at mesophilic conditions was investigated. In addition, the applicability of electrochemical oxidation as an advanced post-treatment for the complete removal of chemical oxygen demand (COD) from the anaerobically treated cheese whey was evaluated. The diluted cheese whey, having a pH of 6.5 and a total COD of 6 g/L, was first treated in a 600-L, pilot-scale up-flow anaerobic sludge blanket (UASB) reactor. The UASB process, which was operated for 87 days at mesophilic conditions (32?±?2 °C) at a hydraulic retention time (HRT) of 3 days, led to a COD removal efficiency between 66 and 97 %, while the particulate matter of the wastewater was effectively removed by entrapment in the sludge blanket of the reactor. When the anaerobic reactor effluent was post-treated over a boron-doped diamond (BDD) anode at 9 and 18 A and in the presence of NaCl as the supporting electrolyte, complete removal of COD was attained after 3–4 h of reaction. During electrochemical experiments, three groups of organochlorinated compounds, namely trihalomethanes (THMs), haloacetonitriles (HANs), and haloketons (HKs), as well as 1,2-dichloroethane (DCA) and chloropicrin were identified as by-products of the process; these, alongside free chlorine, are thought to increase the matrix ecotoxicity to Artemia salina.     

Monitoring the sonochemical degradation of phthalate esters in water using solid-phase microextraction

The sonochemical degradation of aqueous solutions containing low concentrations of six phthalate esters at an ultrasonic frequency of 80 kHz has been investigated. Ultrasonic treatment was found capable of removing the four higher molecular mass phthalates (di-n-butyl phthalate, butylbenzyl phthalate, di-(2-ethylhexyl) phthalate and di-n-octyl phthalate) within 30-60 min of irradiation. The rest (dimethyl phthalate and diethyl phthalate) were more recalcitrant and nearly complete removal could be achieved only after prolonged irradiation times. The relative reactivity of phthalates was explained in terms of their hydrophobicity. Experiments were carried out at an overall initial phthalate concentration of 240 microg l(-1), values of electric power of 75 and 150 W, temperatures of 21 and 50 degrees C and in the presence of NaCl to study the effect of various operating conditions on degradation. Solid-phase microextraction (SPME) coupled with GC-MS proved to be a powerful analytical tool to monitor the sonochemical degradation of phthalate esters at low microg l(-1) concentration levels, minimising the risk of secondary contamination during sample preparation, a major parameter to consider during phthalates analysis. The advantages as well as disadvantages of using SPME are also highlighted.     

Treatment of olive mill effluents Part II. Complete removal of solids by direct flocculation with poly-electrolytes

The pre-treatment of three different olive oil processing effluents by means of direct flocculation (i.e. without prior coagulation) was investigated. Four cationic and two anionic poly-electrolytes were tested and most of them were found capable of removing nearly completely total suspended solids (TSS) as well as reducing considerably the concentration of chemical (COD) and biochemical oxygen demand (BOD(5)) without altering solution pH. Flocculant dosage was crucial to achieve effective separation. For three cationic and one anionic poly-electrolytes, the minimum dosage required to initiate separation was about 2.5-3 g/L. The remaining two poly-electrolytes failed to cause separation even at dosages as high as 7 g/L. Lime and ferric chloride were also tested as reference coagulants and found quite effective in terms of TSS removal although the degree of COD reduction was generally lower than that with poly-electrolytes. However, lime treatment would require greater dosages and longer treatment times than that with poly-electrolytes and would also increase considerably solution pH. A preliminary cost analysis showed that lime treatment for complete solids removal was generally less costly than that with poly-electrolytes presumably due to its low market price. Nonetheless, cost-benefits may be defied by several drawbacks associated with the use of lime.