Automatic searching and evaluation of priority and emerging contaminants in wastewater and river water by stir bar sorptive extraction followed by comprehensive two-dimensional gas chromatography-time-of-flight mass spectrometry

A new analytical method based on stir bar sorptive extraction (SBSE), followed by comprehensive two-dimensional gas chromatography (GCxGC-TOF-MS), has been developed for the automatic searching and evaluation of nonpolar or semipolar contaminants in wastewater and river water. The target compounds selected were 13 personal care products (PCPs), 15 polycyclic aromatic hydrocarbons (PAHs) and 27 pesticides. Excellent results have been obtained in terms of separation efficiency and also in terms of compound identification. Exceptional method detection limits were achieved applying the optimized method, at or below 1 ng/L for most of the compounds in real samples. The reliable confirmation of analyte identity was possible at this low concentration level, even for typically troublesome compounds such as the PAHs. The other validation parameters were good. In addition to obtaining analytical information such as identification and quantification of target analytes, it is also possible to screen for nontarget compounds or unknowns. New contaminants have been identified in the wastewater effluents and river water samples, such as cholesterol and its degradation products, pharmaceuticals, industrial products, other pesticides, and PCPs. The multidimensional information generated by the instrument can also be used by the researchers for contrasting samples and identifying, much more easily, the major differences between samples. We have used this feature to propose studies of comparison between the fingerprinting of different water samples, such as the contamination variation along a river affected by the discharge of urban wastewaters and also the contamination variation over a period of time in the effluent. Results show that the most frequently detected contaminants (and the contaminants detected at higher concentrations) were the PCPs. The musk fragrances galaxolide and tonalid were the most concentrated compounds in the samples. The pesticides and PAHs were present at much lower concentration than PCPs.     

Oxidative and photochemical processes for the removal of galaxolide and tonalide from wastewater

Synthetic musks have been reported in wastewaters at concentrations as high as tens of micrograms per litre. The two most significant polycyclic musk fragrance compounds are 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta(g)-2-benzopyran (HHCB, trade name galaxolide^®) and 7-acetyl-1,1,3,4,4,6-hexamethyltetrahydronaphthalene (AHTN, trade name tonalide^®). We report the result of several irradiation and advanced oxidation processes carried out on samples of the effluent of a wastewater treatment plant located in Alcalá de Henares, Madrid. Wastewater samples were pre-ozonated and spiked with 500 ng/L of tonalide or galaxolide in order to obtain final concentrations in the same order as the raw effluent. The treatments assayed were ozonation with and without the addition of hydrogen peroxide (O₃, O₃/H₂O₂), ultraviolet (254 nm low pressure mercury lamp) and xenon-arc visible light irradiation alone and in combination with ozone (UV, O₃/UV, Xe, O₃/Xe) and visible light photocatalytic oxidation using a Ce-doped titanium dioxide photocatalyst performed under continuous oxygen or ozone gas bubbling (O₂/Xe/Ce-TiO₂, O₃/Xe/Ce-TiO₂). In all cases, samples taken at different contact times up to 15 min were analyzed. An analytical method based on stir bar sorptive extraction (SBSE), followed by comprehensive two-dimensional gas chromatography (SBSE-GC × GC-TOF-MS), was used for the automatic searching and evaluation of the synthetic musks and other nonpolar or semipolar contaminants in the wastewater samples. In all cases tonalide was more easily removed than galaxolide. The best results for the latter (more than 75% removal after 5 min on stream) were obtained from ozonation (O₃) and visible light photocatalytic ozonation (O₃/Xe/Ce-TiO₂). A significant removal of both pollutants (∼60% after 15 min) was also obtained during visible light photocatalysis (O₂/Xe/Ce-TiO₂). UV radiation was able to deplete tonalide (+90%) after 15 min but only reduced the concentration of galaxolide to about half of its initial concentration. The toxicity of treated samples decreased for O₃/UV and O₃/Ce-TiO₂, but increased during irradiation processes UV, Xe and Xe/Ce-TiO₂. Ozone treatments tend to decrease toxicity up to a certain dosage, from which point the presence of toxic transformation products has adverse effects on aquatic microorganisms.     

Prediction of gas hold-up and liquid velocity in airlift reactors using two-phase flow friction coefficients

The overall friction coefficient (K_f) of airlift reactors was estimated using equivalent lengths (L_eq) and friction factors ( f ). The friction factor was calculated taking into account the riser liquid velocity profile corresponding to the two-phase flow and using classical one-phase equations. A previously described model was used to obtain simultaneously both gas hold-up and liquid circulation velocity. The model simulates experimental data obtained in a wide range of configurations of internal (2 and 30 dm³ volume) and external (from 8 to 600 dm³ volume) airlift reactors with Newtonian (water and alcohol solutions) and non-Newtonian (carboxymethylcellulose (CMC) solutions) systems. Com-parison with other models from the literature yielded similar results.     

THEORETICAL PREDICTION OF GAS HOLDUP IN BUBBLE COLUMNS WITH NEWTONIAN AND NON-NEWTONIAN LIQUIDS

A simple model based on an energy balance which takes into account the friction losses at the gas-liquid interface and the slip velocity of single bubble is used to simulate the gas holdup in bubble columns containing Newtonian and non-Newtonian liquids which circulate in both laminar and turbulent flows. Experimental data available from the literature for bubble columns up to 7 m height and 1 m diameter with water and glycerol as Newtonian liquids and different solutions of CMC in a wide range of concentrations as non-Newtonian liquids are simulated with good agreement despite the simplifications made to describe the gas liquid flow regimes. Most of the differences between experimental and calculated gas holdup are justified on the basis of the simplifying assumptions.     

Ozone-based reclamation of an STP effluent

The system ozone and hydrogen peroxide was used to reclaim wastewater from the secondary clarifier from a Sewage Treatment Plant (STP) of Alcalá de Henares (Madrid-Spain). The assays were performed by bubbling a gas mixture of oxygen and ozone, with approximately 24 g Nm(-3) of ozone concentration, through a volume of wastewater samples for 20 minutes at 25 degrees C. The removal of dissolved micropollutants such as Pharmaceutical and Personal Care Products (PPCPs) and Organic Carbon (TOC) was enhanced by adding periodic pulses of hydrogen peroxide while keeping pH above 8.0 throughout the runs. Removal efficiency ratios in the range of 7-26 mg O3/mg TOC and 0.24 mg O3/ng micropollutants at 5 minutes of ozonation were assessed as reference data to reclaim wastewater from STP. The relation between the extent of TOC removed and ozone doses used was related by a second-order kinetic model in which the time-integrated ozone-hydrogen peroxide concentration was included.     

Removal of pharmaceuticals and kinetics of mineralization by O(3)/H(2)O(2) in a biotreated municipal wastewater

The ozonation of an effluent from the secondary clarifier of two Municipal Wastewater Treatment Plants was performed by using alkaline ozone and a combination of ozone and hydrogen peroxide. Alkaline ozonation achieved only a moderate degree of mineralization, essentially concentrated during the first few minutes; but the addition of hydrogen peroxide eventually led to a complete mineralization. The evolution of total organic carbon (TOC) as a measure of the extent of mineralization and the concentration of dissolved ozone were analyzed and linked in a kinetic model whose parameter represented the product of the exposure to hydroxyl radicals and the kinetic constant of indirect ozonation. This rate parameter yielded the highest values during the first part of O(3)/H(2)O(2) runs. The kinetic constant for the decomposition of ozone at the end of the run was also measured and computed for the non-oxidizable water matrix and yielded essentially the same values regardless of whether or not hydrogen peroxide was used. A group of 33 organic compounds, mainly pharmaceuticals and some relevant metabolites present in the wastewater effluents, were evaluated before and after the ozonation process using a liquid chromatography-hybrid triple-quadrupole linear ion trap system (LC-QqLIT-MS). The results demonstrate that the ozonation degrades these compounds with efficiencies of over 99% in most cases, even under low mineralization conditions in alkaline ozonation.     

In vivo efficacies of amoxicillin and cefuroxime against penicillin-resistant Streptococcus pneumoniae in a gerbil model of acute otitis media

The comparative efficacies of amoxicillin and cefuroxime against acute otitis media caused by a penicillin-resistant (MIC, 2 micrograms/ml) Streptococcus pneumoniae strain were assessed in a gerbil model by challenging each ear with 10(7) bacteria through transbullar instillation. Each antibiotic was tested at two doses (5 and 20 mg/kg of body weight) administered at 2, 10, and 18 h postinoculation. Samples were obtained from the middle ear (ME) on days 3 and 7 postinoculation for determination of bacterial counts. Only amoxicillin, at both doses, was able to significantly halt the weight loss in animals, reducing both the number of culture-positive animals and the bacterial concentration in ME samples versus the values for untreated animals. Comparison of the efficacies between the antibiotics, determined by their ability to achieve culture-negative ME specimens, showed that amoxicillin at 5 mg/kg was significantly more active than cefuroxime at the same dose. The use of higher doses of either amoxicillin or cefuroxime did not produce significantly better results than those obtained with the lower dose but caused a greater inflammatory response. The more favorable results obtained with amoxicillin compared with those obtained with cefuroxime could be related to the antimicrobial susceptibility of the pneumococcal strain (MICs and minimum bactericidal concentrations of 1 and 1 microgram/ml and 4 and 4 micrograms/ml for amoxicillin and cefuroxime, respectively) as well as to the better pharmacokinetic parameters obtained with amoxicillin.     

Enhancement of dibenzothiophene biodesulfurization using β-cyclodextrins in oil-to-water media

It has been reported that biodesulfurization (BDS) of dibenzothiophene (DBT) in oil-to-water emulsions is carried out by growing cells of the aerobic Rhodococcus erythropolis IGTS8 strain and developing the so-called 4S desulfurization pathway. On adding β-cyclodextrins, it is possible to improve the BDS yields, increase the diffusion of DBT into the aqueous phase or avoid the HBP accumulation. Moreover, by using greater biocatalyst initial concentrations and adding 15 ppm of β-cyclodextrin, a very high BDS yield has been observed, but the presence of mass transfer limitations and the inhibition effects were not satisfactorily avoided. The Haldane kinetic model agreed well with the experimental results obtained, and the values of the kinetic parameters were determined.     

Kinetics and Mechanism of Catalytic Ozonation of Aqueous Pollutants on Metal Oxide Catalysts

The catalytic ozonation of fenofibric and clofibric acids and the herbicides atrazine and linuron was studied using titanium dioxide, alumina, and manganese oxide supported on activated alumina and on silica SBA-15. The organics studied did not adsorb significantly either in wastewater or in phosphate-buffered water. The catalysts did not modify the rate of the hydroxyl-mediated ozonation with respect to the homogeneous value. The mode of action of metal oxide catalysts would be an enhanced generation of oxidant species from the catalytic decomposition of ozone. All catalysts increased the efficiency in the production of hydroxyl radicals from ozone.     

Energy efficiency for the removal of non-polar pollutants during ultraviolet irradiation,visible light photocatalysis and ozonation of a wastewater effluent

This study aims to assess the removal of a set of non-polar pollutants in biologically treated wastewater using ozonation, ultraviolet (UV 254 nm low pressure mercury lamp) and visible light (Xe-arc lamp) irradiation as well as visible light photocatalysis using Ce-doped TiO₂. The compounds tracked include UV filters, synthetic musks, herbicides, insecticides, antiseptics and polyaromatic hydrocarbons. Raw wastewater and treated samples were analyzed using stir-bar sorptive extraction coupled with comprehensive two-dimensional gas chromatography (SBSE–CG × GC–TOF–MS). Ozone treatment could remove most pollutants with a global efficiency of over 95% for 209 μM ozone dosage. UV irradiation reduced the total concentration of the sixteen pollutants tested by an average of 63% with high removal of the sunscreen 2-ethylhexyl trans-4-methoxycinnamate (EHMC), the synthetic musk 7-acetyl-1,1,3,4,4,6-hexamethyltetrahydronaphthalene (tonalide, AHTN) and several herbicides. Visible light Ce–TiO₂ photocatalysis reached ∼70% overall removal with particularly high efficiency for synthetic musks. In terms of power usage efficiency expressed as nmol kJ⁻¹, the results showed that ozonation was by far the most efficient process, ten-fold over Xe/Ce–TiO₂ visible light photocatalysis, the latter being in turn considerably more efficient than UV irradiation. In all cases the efficiency decreased along the treatments due to the lower reaction rate at lower pollutant concentration. The use of photocatalysis greatly improved the efficiency of visible light irradiation. The collector area per order decreased from 9.14 ± 5.11 m² m⁻³ order⁻¹ for visible light irradiation to 0.16 ± 0.03 m² m⁻³ order⁻¹ for Ce–TiO₂ photocatalysis. The toxicity of treated wastewater was assessed using the green alga Pseudokirchneriella subcapitata. Ozonation reduced the toxicity of treated wastewater, while UV irradiation and visible light photocatalysis limited by 20–25% the algal growth due to the accumulation of reaction by-products. Three transformation products were identified and tracked along the treatments.