Javier Rivas

Cheese whey management: a review.

Cheese whey is simultaneously an effluent with nutritional value and a strong organic and saline content. Cheese whey management has been focused in the development of biological treatments without valorization; biological treatments with valorization; physicochemical treatments and direct land application. In the first case, aerobic digestion is reported. In the second case, six main processes are described in the literature: anaerobic digestion, lactose hydrolysis, fermentation to ethanol, hydrogen or lactic acid and direct production of electricity through microbial fuel cells. Thermal and isoelectric precipitation, thermocalcic precipitation, coagulation/flocculation, acid precipitation, electrochemical and membrane technologies have been considered as possible and attractive physicochemical processes to valorize or treat cheese whey. The direct land application is a common and longstanding practice, although some precautions are required. In this review, these different solutions are analyzed. The paper describes the main reactors used, the influence of the main operating variables, the microorganisms or reagents employed and the characterizations of the final effluent principally in terms of chemical oxygen demand. In addition, the experimental conditions and the main results reported in the literature are compiled. Finally, the comparison between the different treatment alternatives and the presentation of potential treatment lines are postulated.

Cheese whey wastewater: Characterization and treatment

Cheese whey wastewater (CWW) is a strong organic and saline effluent whose characterization and treatment have not been sufficiently addressed. CWW composition is highly variable due to raw milk used, the fraction of non valorized cheese whey and the amount of cleaning water used. Cheese whey wastewater generation is roughly four times the volume of processed milk. This research tries to conduct an exhaustive compilation of CWW characterization and a comparative study between the different features of CWW, cheese whey (CW), second cheese whey (SCW) and dairy industry effluents. Different CWW existing treatments have also been critically analyzed. The advantages and drawbacks in aerobic/anaerobic processes have been evaluated. The benefits of physicochemical pre-stages (i.e. precipitation, coagulation-flocculation) in biological aerobic systems are assessed. Pre-treatments based on coagulation or basic precipitation might allow the application of aerobic biodegradation treatments with no dilution requirements. Chemical precipitation with lime or NaOH produces a clean wastewater and a sludge rich in organic matter, N and P. Their use in agriculture may lead to the implementation of Zero discharge systems.

Kinetics of Heterogeneous Catalytic Ozone Decomposition in Water on an Activated Carbon

Abstract Ozone decomposition in water in the presence of an activated carbon has been studied. Variables investigated were agitation speed, carbon particle size, temperature and pH. In all cases, the presence of activated carbon improved the ozone decomposition rate. Between pH 2 and 7 the ozone decomposition rate due to both the homogeneous and heterogeneous mechanisms hardly varied while a significant increase was noticed with increasing pH. A kinetic study based on a Langmuir-Hinselwood type mechanism for the heterogeneous surface reaction was undertaken. According to this mechanism the heterogeneous ozone decomposition kinetics can be simplified to follow a first order process. Fit of experimental results to the kinetic equations derived from the mechanism allowed for the determination of the apparent first order rate constants of the ozone surface heterogeneous reaction and adsorption equilibrium constants.

Aqueous degradation of atrazine and some of its main by-products with ozone/hydrogen peroxide

This laboratory study was designed to investigate the removal of atrazine (ATZ) and its first main by-products, deethylatrazine (DEA) and deisopropylatrazine (DIA) by O 3 /H 2 O 2 . At least 76% of the oxidation rate of atrazine is due to free radical reactions. At neutral pH and 20°C, an initial hydrogen peroxide concentration of 10 -3 M is optimum to reach a maximum oxidation rate of these compounds. Experimental results of oxidation in the presence of high hydrogen peroxide concentrations allow the mass transfer coefficient of ozonation to be determined. This coefficient, reactor flow analysis and kinetic data obtained have been applied to mol balance equations of atrazine, deisopropylatrazine, deethylatrazine, ozone (both in the gas and water) and hydrogen peroxide to obtain their corresponding concentrations at different conditions.

Treatment of Cheese Whey Wastewater: Combined Coagulation−Flocculation and Aerobic Biodegradation

Cheese wastewater has been treated by means of a coagulation-flocculation process. Three different coagulants have been used, namely, FeSO(4), Al(2)(SO(4))(3), and FeCl(3). When FeSO(4) was used, the optimum conditions were obtained using 250 ppm of the salt at pH 8.5. At these conditions, 50 and 60% of chemical oxygen demand (COD) and biological oxygen demand (BOD) were reduced, respectively. Al(2)(SO(4))(3) achieved slightly lower reductions of COD and BOD; however, the amount needed was significantly higher (1000 ppm). When FeCl(3) was added, similar results to those obtained with FeSO(4) were experienced; again, 250 ppm was enough to eliminate COD and BOD contents in the range of 40-60%, depending upon operating conditions. The sludge formed in the coagulation-flocculation process did show acceptable settling properties, which is crucial in settling tank design. A first approach to sedimentation tank design is also conducted on the basis of experimental results. The aerobic biodegradation of cheese whey wastewater achieves the reduction of the main contaminant indicators (COD and BOD) to values close to 100%; however, effluents coming from the coagulation-flocculation pre-stage necessitate half of the time required by the non-pretreated raw wastewater.

Ozone treatment of PAH contaminated soils: Operating variables effect

A three-level full factorial design has been conducted to assess the influence of gas flow-rate, ozone concentration and reaction time on the remediation of soil contaminated with four PAHs (namely acenaphthene, phenanthrene, anthracene and fluoranthene). Under the operating conditions investigated, reaction time and ozone concentration seem to exert a slight positive effect, whereas gas flow-rate does not affect the process efficiency. Average conversions (related to non-ozonated samples) are in the proximity of 50, 70, 60 and 100% for acenaphthene, phenanthrene, anthracene and fluoranthene, respectively. A high conversion percentage is obtained in the first minutes of the process. Ozone decomposition on soil surface can be modelled by its reactions with easily oxidizable organic matter, recalcitrant ozonation intermediates and inorganic active sites.

Aerobic Biodegradation of Precoagulated Cheese Whey Wastewater

Prior to the application of an aerobic biological process, cheese whey wastewater has been pretreated by means of a precipitation stage by adding either NaOH or CaOH2. Both precipitating agents reduce roughly 50% of the raw wastewater chemical oxygen demand (COD). The sludge generated in the prestage shows acceptable settling properties, although solids from the CaOH2-treated effluent are better separated from the liquid bulk than those formed in NaOH-processed wastewater. In both situations, the presedimentation stage renders a supernatant more prone to biodegradation than the untreated effluent. The previous statement is corroborated by the determination of some biological kinetic parameters. Under the operating conditions used in this work, sludge generation after the biological process is reduced to a minimum. The sludge generated shows good settling properties, especially for those experiments in which CaOH2 has previously been added.

UV-C photolysis of endocrine disruptors. The influence of inorganic peroxides

Norfloxacin, doxycycline and mefenamic acid have been photolysed with UV-C radiation (254 nm) in the presence and absence of inorganic peroxides (hydrogen peroxide or sodium monopersulfate). Quantum yields in the range (1.1-4.5)x10(-3) mol Einstein(-1) indicate the low photo-reactivity of these pharmaceuticals. Inorganic peroxides considerably enhanced the contaminants conversion, although no appreciable mineralization could be obtained. A simplistic reaction mechanism for the hydrogen peroxide promoted experiments allowed for a rough estimation of the rate constant between hydroxyl radicals and norfloxacin (k>1 x 10(9)M(-1)s(-1)), doxycycline (k>1.5 x 10(9)M(-1)s(-1)) and mefenamic acid (k>11.0 x 10(9)M(-1)s(-1)).

Ozonation of the pharmaceutical compound ranitidine: reactivity and kinetic aspects.

Ranitidine has been ozonated under different operating conditions of pH, applied ozone dose, initial ranitidine concentration and presence or absence of free radical inhibitors. Results of ranitidine evolution with time indicate a high reactivity of this compound with molecular ozone. Mineralization levels achieved in the order of 20-25% suggest that the (CH3)2-N-CH2- moiety bonded to the furan ring could be separated from the rest of the ranitidine structure and further mineralized. Only alkaline conditions (pH=11) are capable of increasing TOC conversion up to values close to 70%. Determination of the direct ozonation rate constant for ranitidine by means of competitive kinetics reveals an unacceptable dependence of the aforementioned constant with the reference compound reactivity. It is hypothesised that only reference compounds with reactivity similar to the target species should be used.

Application of advanced oxidation processes to doxycycline and norfloxacin removal from water

Doxycycline (Dxy) and Norfloxacin (Nfx) have been oxidized by means of different technologies of increasing complexity. Preliminary experiments showed that activated carbon adsorption (1.0 g L−1) of these antibiotics (CAntibiotic = 5 × 10−5 M) led to a 60 and 85 % of total organic carbon (TOC) removal, however, a significant decrease in adsorption capacity was experienced after several reuses of the adsorbent. UV-C irradiation of Dxy (20 % removal in 2 h) or Nfx (90 % removal in 2 h) did not affect the initial TOC content of the solution while single ozonation (CO3 gas inlet concentration = 15.0 ppm) led to the instantaneous disappearance of the parent compounds while TOC conversion values in the proximity of 40 % were obtained. Complex systems based on the combination of ozone, UV-C radiation, titanium dioxide and activated carbon led to similar TOC removals of the order of 70 and 65 % for Dxy and Nfx, respectively. An attempt has been made to calculate the quantum yield and direct ozonation rate constants for doxycycline and norfloxacin. Additionally, the best systems, i.e., the O3 and O3/UV-C processes, have been simulated by a pseudoempirical model by considering TOC as a surrogate parameter.