Fate Of By-products Research Articles

Pt Modified Heterogeneous Catalysts Combined with Ozonation for the Removal of Diclofenac from Aqueous Solutions and the Fate of by-Products

The degradation of the pharmaceutical compound diclofenac in an aqueous solution was studied with an advanced oxidation method, catalytic ozonation. Diclofenac was destroyed in a few minutes by ozonation but several long-lasting degradation by-products were formed. For this reason, the combination of heterogeneous catalysts and ozonation was applied to eliminate them completely. The kinetics of the diclofenac degradation and the formation of by-products were thoroughly investigated. Loading of Pt on the catalysts resulted in an improvement of the activity. The Mesoporous Molecular Sieves (MCM) were one of the promising catalysts for the degradation of organic pollutants. In this study, six heterogeneous catalysts were screened, primarily MCM-22-100 catalysts with different Pt concentrations loaded via the evaporation-impregnation (EIM) method, and they were applied on the degradation of diclofenac. It was found that the presence of Pt improved the degradation of diclofenac and gave lower concentrations of by-products. The 2 wt % Pt-H-MCM-22-100-EIM demonstrated the highest degradation rate compared to the proton form, 1% or 5 wt % Pt concentration, i.e., an optimum was found in between. Pt-H-Y-12-IE and Pt-γ-Al2O3 (UOP)-IMP catalysts were applied and compared with the MCM-22 structure. Upon use of both of these catalysts, an improvement in the degradation of diclofenac and by-products was observed, and the 2 wt % Pt-H-MCM-22-100-EIM illustrated the maximum activity. All important characterization methods were applied to understand the behavior of the catalysts (X-ray powder diffraction, transmission electron microscopy, nitrogen physisorption, scanning electron microscopy, energy dispersive X-ray micro-analyses, pyridine adsorption-desorption with FTIR spectroscopy, X-ray photoelectron spectroscopy). Finally, leaching of Pt and Al were analyzed by inductively coupled optical emission spectrometry.

Electrochemical removal of Terbuthylazine:Boron-Doped Diamond anode coupled with solid polymer electrolyte

Terbuthylazine (TBA) has replaced atrazine in many EU countries, becoming one of the most frequently detected pesticides in natural waters. TBA is a compound of emerging concern, due to its persistence, toxicity and proven endocrine disruption activity to wildlife and humans. Techniques applied in water treatment plants remove only partially this herbicide and poor attention is given to the generation and fate of by-products, although some of them have demonstrated an estrogenic activity comparable to atrazine. This paper summarizes the environmental occurrence of TBA and its main metabolite desethylterbuthylazine and reports the performance of an innovative electrochemical cell equipped with a solid polymer electrolyte (SPE) sandwiched between a Ti/RuO2 cathode and a Boron-Doped Diamond anode, operating at constant current, in the treatment of an aqueous solution of TBA. The herbicide removal in the first 30 min of treatment increases from 42% to 92% as the applied current is increased from 100 to 500 mA. The rate of degradation at 500 mA decreases between 30 and 60 min, with a final abatement of 97%. An 89% removal was reached at 100 mA when the initial TBA concentration was raised from 0.1 to 4 mg L−1 and less than 1% of the herbicide was converted in desethylterbuthylazine and minor metabolites. No chemicals are needed, no sludge is produced. Further research is encouraged, as this technology may be promising for the achievement of a zero-discharge removal of different emerging pollutants as pesticides, pharmaceuticals and personal care products.

Mechanism and Significance of Chlorophyll Breakdown

Chlorophyll breakdown is the most obvious sign of leaf senescence and fruit ripening. A multistep pathway has been elucidated in recent years that can be divided into two major parts. In the first phase, which commonly is active in higher plants, chlorophyll is converted via several photoreactive intermediates to a primary colorless breakdown product within the chloroplast. The second part of chlorophyll breakdown takes place in the cytosol and the vacuole. During this phase, the primary colorless intermediate is modified in largely species-specific reactions to a number of similar, yet structurally different, linear tetrapyrrolic products that finally are stored within the vacuole of senescing cells. To date, most of the biochemical reactions of the first phase of chlorophyll breakdown have been elucidated and genes have been identified. By contrast, mechanisms of catabolite transport and modification during the second phase are largely unknown. This review summarizes the current knowledge on the biochemical reactions involved in chlorophyll breakdown, with a special focus on the second-phase reactions and the fate of by-products that are released from chlorophyll during its breakdown.

Formation and fate of chlorination by-products in reverse osmosis desalination systems

Chlorination by-products may be formed during pretreatment or posttreatment disinfection in reverse osmosis (RO) desalination systems, potentially posing health, aesthetic and ecological risks. To assess the formation and fate of by-products under different conditions likely to be encountered in desalination systems, trihalomethanes, dihaloacetonitriles, haloacetic acids, and bromophenols were analyzed in water samples from a pilot-scale seawater desalination plant with a chlorine pretreatment system and in benchscale experiments designed to simulate other feed water conditions. In the pilot plant, RO rejection performance as low as 55% was observed for neutral, low-molecular-weight by-products such as chloroform or bromochloroacetonitrile. Benchscale chlorination experiments, conducted on seawater from various locations indicated significant temporal and spatial variability for all by-products, which could not be explained by measured concentrations of organic carbon or bulk parameters such as SUVA 254. When desalinated water was blended with freshwater, elevated concentrations of bromide in the blended water resulted in dihaloacetonitrile concentrations that were higher than those expected from dilution. In most situations, the concentration of chlorination by-products formed from continuous chlorination of seawater or blending of desalinated water and freshwater will not compromise water quality or pose significant risks to aquatic ecosystems.

UV Photolysis of Trichloroethylene: Product Study and Kinetic Modeling

Direct UV photolysis of trichloroethylene (TCE) in dilute aqueous solution generated chloride ions as a major end product and several reaction intermediates, such as formic acid, di- and monochloroacetic acids, glyoxylic acid, and, to a lesser extent, mono- and dichloroacetylene, formaldehyde, dichloroacetaldehyde, and oxalic acid. Under prolonged irradiation, these byproducts underwent photolysis, and a high degree of mineralization (approximately 95%) was achieved. TCE decays through the following major pathways: (1) TCE + h nu --> ClCH=C*Cl + Cl*; (2) TCE (H2O) + h nu --> ClCH(OH)-CHCl2; (3) TCE + h nu --> HC[triple bond]CCl + Cl2; (4) TCE + h nu --> ClC[triple bond]CCl + HCl; (5) TCE + Cl* --> Cl2HC-C*Cl2. A kinetic model was developed to simulate the destruction of TCE and the formation and fate of byproducts in aqueous solution under irradiation with polychromatic light. By fitting the experimental data, the quantum yields for the four photolysis steps were predicted as phi(1) = 0.13, phi(2) = 0.1, phi(3) = 0.032, and phi(4) = 0.092, respectively. The reaction mechanism proposed for the photodegradation of TCE accounts for all intermediates that were detected. The agreement between the computed and experimental patterns of TCE and reaction products is satisfactory given the complexity of the reaction mechanism and the lack of photolytic kinetic parameters that are provided in the literature.