Solid-phase microextraction to monitor the sonochemical degradation of polycyclic aromatic hydrocarbons in water

Solid-phase microextraction (SPME) coupled with GC-MS has been used to monitor the degradation of polycyclic aromatic hydrocarbons (PAHs) by ultrasound treatment. Immersion SPME sampling enabled the fast and solventless extraction of target contaminants at the low microg l(-1) concentration level. The developed protocol was found to be linear in the concentration range from 0.1 to 50 microg l(-1) for most target analytes, with the limits of detection ranging between 0.01 and 0.70 microg l(-1) and the relative standard deviations between 4.31 and 27%. The developed SPME protocol was used to follow concentration profiles of aqueous solutions containing 16 PAHs, which were subject to low frequency ultrasonic irradiation. At the conditions employed in this study (80 kHz of ultrasound frequency, 130 W l(-1) of applied electric power density, 30 microg l(-1) of initial concentration for each of the 16 PAHs), sonochemical treatment was found capable of destroying the lower molecular weight PAHs (naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene and pyrene) within 120-180 min of irradiation. The higher molecular weight PAHs were more recalcitrant to ultrasound treatment.     

Advanced Oxidation Processes for Water and Wastewater Viral Disinfection. A Systematic Review

Food and Environmental Virology - Water and wastewater virological quality is a significant public health issue. Viral agents include emerging and re-emerging pathogens characterized by extremely...     

Removal of faecal indicator pathogens from waters and wastewaters by photoelectrocatalytic oxidation on TiO2/Ti films under simulated solar radiation

Purpose

The disinfection efficiency of water and secondary treated wastewater by means of photoelectrocatalytic oxidation (PEC) using reference strains of Enterococcus faecalis and Escherichia coli as faecal indicators was evaluated. Operating parameters such as applied potential (2?C10?V), initial bacterial concentration (10³?C10⁷?CFU/mL), treatment time (up to 90?min) and aqueous matrix (pure water and treated effluent) were assessed concerning their impact on disinfection.

Methods

PEC experiments were carried out using a TiO₂/Ti film anode and a zirconium cathode in the presence of simulated solar radiation. Bacterial inactivation was monitored by the culture method and real-time SYBR green PCR.

Results

A 6.2 log reduction in E. faecalis population was achieved after 15?min of PEC treatment in water at 10?V of applied potential and an initial concentration of 10⁷?CFU/mL; pure photocatalysis (PC) led to only about 4.3 log reduction, whilst negligible inactivation was recorded when the respective electrochemical oxidation process was applied (i.e. without radiation). PEC efficiency was generally improved increasing the applied potential and decreasing initial bacterial concentration. Regarding real wastewater, E. coli was more susceptible than E. faecalis during treatment at a potential of 5?V. Wastewater disinfection was affected by its complex composition and the contained mixed bacterial populations, yielding lower inactivation rates compared to water treatment. Screening the results obtained from both applied techniques (culture method and real-time PCR), there was a discrepancy regarding the recorded time periods of total bacterial inactivation, with qPCR revealing longer periods for complete bacterial reduction.

Conclusions

PEC is superior to PC in terms of E. faecalis inactivation presumably due to a more efficient separation and utilization of the photogenerated charge carriers, and it is mainly affected by the applied potential, initial bacterial concentration and the aqueous matrix.     

Survival of total coliforms in lawn irrigated with secondary wastewater and chlorinated effluent in the Mediterranean region.

Pregrown, two-month-old lawn was layered in 12 large square pots with an area of 0.25 m2 each, filled with a mixture of topsoil, peat, and sand. In late July, in the heart of the Mediterranean summer, the pots were divided into two groups, with six pots per group. On four different occasions, the pots in each group were sprinkled (surface irrigation) with 2 L of either secondary-treated wastewater (STW, group A) or chlorinated effluent (CHE, group B). Wastewater application always took place at 0700 hours. Samples of the surface soil and grass from each pot were collected at the following times: before irrigation, immediately after irrigation, two hours later (0900 hours), and four hours later (1100 hours). In the samples collected, the number of total coliforms per gram was measured using standard microbiological analyses. Temperature and sunlight intensity were also monitored. There was an increase in the coliforms population in soil and grass samples of both groups immediately after the wastewater application. In group A, the mean number of coliforms recorded in the soil samples reached mean values higher than 5000 cfu/g compared to 312 cfu/g recorded before application. The increase in group B was smaller but still significant. Two hours later, the number of coliforms was reduced substantially in all samples (e.g., group A, soil samples 477 cfu/g). Coliform inactivation is thought to result from the effect of temperature and mainly sunlight. However, four hours after application (1100 hours), there was a noticeable increase in the coliform number again, in all sample categories of both groups. Coliform reactivation could be a result of shadowing effect resulting from the thick foliage of the grass, where the microorganisms were protected by the sunlight radiation and regrowth in a friendly environment (especially of the soil) where moisture and nutrients were present. This, in addition to the fact that coliforms seemed to retain a sizable population between applications, results in three conclusions: (1) coliforms can survive in grass and soil for a substantial period of time, recovering from the destructive effect of chlorination, (2) use of STW, even during the Mediterranean summer, could result in a substantial "contamination" of lawns, without any proof that sun and temperature can reduce the coliform number, and (3) intense sunlight (up to 68 000 lux) was far more effective in coliform suppression than elevated temperature (up to 38 degrees C).     

Removal of Cinnamic Acid Derivatives from Aqueous Effluents by Fenton and Fenton-like Processes as an Alternative to Direct Biological Treatment

The removal of various phenolic acids (p-coumaric, caffeic and ferulic acids), typically found in wastewaters of agricultural origin, from model effluents by chemical and biological means has been investigated. Chemical oxidation processes comprising hydrogen peroxide and a homogeneous or heterogeneous copper or iron catalyst were employed over a wide range of experimental conditions. Chemical oxidation is capable of removing most of the total organic carbon initially present in the effluent at relatively mild treatment conditions (i.e. reaction times up to 120 min and temperatures up to 80°C), while removal rates generally increase with increasing temperature, H₂O₂ and catalyst concentrations. The anaerobic degradability and toxicity of p-coumaric acid has been assessed using the biochemical methane potential and anaerobic toxicity assay respectively. p-Coumaric acid, at concentrations below about 1 g/L, is not toxic against methanogens and slowly degrades over a period of about 35 days at 35°C. In light of this, chemical oxidation may provide a promising alternative to direct biological treatment for either the partial or complete removal of phenolic acids at reasonable treatment times; the implications for wastewater treatment are discussed.     

Analysis of polycyclic aromatic hydrocarbons in wastewater treatment plant effluents using hollow fibre liquid-phase microextraction

A simple and efficient method for the enrichment of low molecular weight polycyclic aromatic hydrocarbons (PAHs) in effluents originating from wastewater treatment plants is presented here. The proposed protocol couples the recently introduced hollow fibre liquid-phase microextraction (LPME) method with gas chromatography-mass spectrometry. Method parameters were controlled and the optimised experimental conditions were: 5 ml aqueous samples, containing 2.5% NaCl w/v, stirred at 1000 rpm, extracted with toluene for 15 min. The developed protocol yielded a linear calibration curve in the concentration range from 0.5 to 50 microg l(-1) for all target analytes (namely acenaphthene, phenanthrene, fluoranthene and pyrene) and limits of detection in the low microg l(-1) level (0.005-0.011 microg l(-1)). The repeatability and inter-day precision of the method varied between 2.7% and 11.3% and 7.9% and 14.4% respectively. The relative recoveries from different types of natural water samples revealed that matrix had a small effect on the hollow fibre LPME process. The developed method was then applied for the determination of PAHs contamination in effluent samples taken from two major municipal wastewater treatment plants. The results were compared with those obtained with solid-phase microextraction. The ability of both microextraction methods to concentrate organic analytes was demonstrated as both methods confirmed the presence of PAHs as well as of phthalates in the examined effluent samples.     

Kinetics of low frequency sonodegradation of linear alkylbenzene sulfonate solutions

The decomposition of sodium dodecylbenzene sulfonate (SDBS) in water by means of ultrasound irradiation at 20kHz was investigated. Experiments were conducted at surfactant concentrations of 175, 260 and 350 mg l(-1), liquid volumes of 120, 170 and 220 ml, temperatures of 20, 30 and 45 degrees C and applied power of 40, 80 and 125 W. The extent of degradation was followed monitoring substrate and organic carbon concentrations, while hydrogen peroxide concentration was also measured; the latter is a product of water sonolysis due to hydroxyl radical recombination. 80% SDBS conversion was achieved after 120 min of sonication at 125 W and 30 degrees C; nonetheless, SDBS and its degradation intermediates proved difficult to oxidise as only about 20-25% of the initial carbon content was transformed to carbon dioxide. At the initial stages of the reaction, degradation rate appears to be only weakly dependent on the substrate concentration with the rate increasing from 3.1 to 4 mg l(-1)min(-1) with increasing concentration from 175 to 350 mg l(-1). Degradation appears to occur at the bubble-liquid interface through hydroxyl radical-mediated reactions whose role was established by performing experiments in the presence of radical scavengers, namely potassium bromide and sodium benzoate. Degradation rates increased with increasing power and decreasing temperature and volume.     

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.