Water disinfection using hydrogen peroxide with fixed bed hematite catalyst - kinetic and activity studies.

A lab-scale reactor with a fixed-bed hematite catalyst for the effective decomposition of H2O2 and bacteria inactivation was designed. The bactericidal effect is the largest at a low initial bacterial count of 2·103 CFU/L, which is typical for natural surface waters. When using a 5 mM H2O2 solution and a residence time of 104 min, the reduction in the number of E. coli bacteria is about 3.5-log. At a higher initial bacterial count of 1-2·104 CFU/L, a 5 mM H2O2 solution reduces the bacteria number by about 4-log. The H2O2 decomposition follows the log-linear kinetics of a first-order reaction while the bacterial inactivation does not. The kinetics of bacterial inactivation was described using the Weibull model in the modified form: log10(N0/N) = b · tn. The values of the non-linearity parameter n were found to be lower than 1, indicating that bacterial inactivation slows down over time. With increasing initial H2O2 concentration, the rate parameter b increases while the non-linearity parameter n decreases. With increasing temperature, both parameters increase. The stability of the catalyst has been proved by XRD, FTIR, SEM, and ICP-OES. The concentration of iron leaching into water during disinfection is much lower than the limit declared by WHO for iron in drinking water. The results show that technical-grade hematite is a promising Fenton-like catalyst for water disinfection. The fixed-bed reactor can be the basis of the mobile installations for water purification in emergencies.

Coagulation of Hydrophobic Ionic Associates of Cetyltrimethylammonium Bromide and Carrageenan.

In aqueous solutions, cetyltrimethylammonium cations bind to carrageenan polyanions, and the resulting ionic associates form macroscopic aggregates due to hydrophobic interaction. At certain ratios of cetyltrimethylammonium to carrageenan, the resulting colloidal particles auto-flocculate. According to visual observations, the ratio ranges from 1 to 3 mmol/g; otherwise the suspensions are stable. By measuring the sedimentation rate and particle size distribution, the most extensive flocculation was found to be from 1.7 to 2.3 mmol/g. The ratio corresponding to the fastest auto-flocculation was precisely determined by titrating the reagents with small increments and recording the turbidity. The turbidimetric titration plots contain distinct break points corresponding to the most extensive flocculation. These break points occur at the same ratio of carrageenan to cetyltrimethylammonium over a wide range of reagent concentrations. The precise values of the critical ratio were found to be 1.78 and 1.53 mmol/g, respectively, during the titration of cetyltrimethylammonium with carrageenan and vice versa. The number of anionic sulfate groups in carrageenan was measured by ICP OES and found to be 1.35 mmol/g. This value is consistent with the critical ratio of the auto-flocculation.

Determination of Calcium in Meat Products by Automatic Titration with 1,2-Diaminocyclohexane-N,N,N',N'-tetraacetic Acid.

Mechanically separated meat (MSM) is a by-product of the poultry industry that requires routine quality assessment. Calcium content is an indirect indicator of bone debris in MSM but is difficult to determine by EDTA titration due to the poor solubility of calcium phosphate. Therefore, 1,2-diaminocyclohexane-N,N,N',N'-tetraacetic acid was used instead, which has two orders of magnitude higher affinity for calcium ions. In addition, the auxiliary complexing agents triethanolamine and Arsenazo III, an indicator that is sensitive to low calcium concentrations, were used. Automatic titration endpoint detection was performed using an immersion probe at 660 nm. It has been shown that the color change in Arsenazo III can also be read with an RGB camera. The CDTA titration procedure has been tested on commercial Bologna-type sausages and the results were in line with AAS and ICP reference data. The content of calcium in sausages turned out to be very diverse and weakly correlated with the content of MSM. The tested MSM samples had a wide range of calcium content: from 62 to 2833 ppm. Calcium-rich poultry by-products include fat and skin (115 to 412 ppm), articular cartilage (1069 to 1704 ppm), and tendons (532 to 34,539 ppm). The CDTA titration procedure is fully suitable for small meat processing plants due to its simplicity of use and low cost.

Cobalt ferrite as an electromagnetically boosted metal oxide hetero-Fenton catalyst for water treatment.

The cobalt ferrite Fenton catalysts were obtained by the flow co-precipitation method. FTIR, XRD, and Mössbauer spectroscopy confirmed the spinel structure. The crystallite size of the as-synthesized sample is 12 nm, while the samples annealed at 400 and 600 °C have crystallite sizes of 16 and 18 nm, respectively. The as-synthesized sample has a grain size of 0.1-5.0 µm in size, while the annealed samples have grain sizes of 0.5 µm-15 µm. The degree of structure inversion ranges from 0.87 to 0.97. The catalytic activity of cobalt ferrites has been tested in the decomposition of hydrogen peroxide and the oxidation of caffeine. The annealing of the CoFe2O4 increases its catalytic activity in both model reactions, with the optimal annealing temperature being 400 °C. The reaction order has been found to increase with increasing H2O2 concentration. Electromagnetic heating accelerates the catalytic reaction more than 2 times. As a result, the degree of caffeine decomposition increases from 40% to 85%. The used catalysts have insignificant changes in crystallite size and distribution of cations. Thus, the electromagnetically heated cobalt ferrite can be a controlled catalyst in water purification technology.

Structure and Flocculation of Ion Associates of Carrageenan and Poly(diallyldimethylammonium chloride) Depending on the Component Ratio.

Carrageenan is a polysaccharide of a plant origin, commonly used as a thickening and gelling agent in the food, pharmaceutical, and cosmetic industries. Due to the negative charges of its sulfate groups, carrageenan macromolecules strongly interact with oppositely charged polyions. The ionic complexes of carrageenan with poly(diallyldimethylammonium chloride) were obtained at the molar ratios 4:1, 2;1, 1:1, 1:2, and 1:4. The structure and characteristics of the polyanion-polycation associates were studied by XRD, IR, optical microscopy, and via sedimentation and particle size measurements. It was found that the suspended particles flocculate and settle fastest when the molar ratio of the polyions is near 1:1. Turbidimetric titration experiments enabled us to measure the molar ratio of cationic to anionic groups at the onset of flocculation, and the value in question was found to be 1:1.32. In other words, a mass of 511 mg carrageenan corresponds to one millimole of ester sulfate (monobasic) groups. The measurement of the onset of flocculation has been employed for the accurate determination of carrageenan in real samples of food products. The color and turbidity of the sample do not interfere with the determination results.

Eco-friendly synthesis of cobalt-zinc ferrites using quince extract for adsorption and catalytic applications: An approach towards environmental remediation.

Cobalt-zinc ferrite nanoparticles were synthesized using environmentally friendly approach with quince extract as a reducing agent. Crystal structure and morphology of the obtained materials were studied by XRD, SEM-EDS, Mössbauer and IR spectroscopy. The synthesized nanoparticles have a cubic spinel structure and crystallite size ranging from 5 to 9 nm. The infrared spectra contain characteristic absorption bands for the MA-O (∼560 cm-1) and MB-O bonds (∼420 cm-1). Force constants were calculated for both tetrahedral and octahedral bonds. As the Co content increases, the force constant for the tetrahedral bond increases and the force constant for the octahedral bond decreases. The obtained ferrite nanoparticles have good magnetization as shown by VSM (in the range from 36 to 67 emu/g). Magnetic nanoparticles CoxZn1-xFe2O4 were also tested for induction heating with electromagnetic field. The sample with x (Co) = 0.4 has the highest specific absorption rate. The synthesized samples were tested as adsorbents using the Congo Red dye as model pollutant. The best adsorbent was pure zinc ferrite with the adsorption capacity of 24.7 mg/g. The catalytic activity of the obtained ferrites for the decomposition of H2O2 was studied as well. The most active catalyst was pure cobalt ferrite. Probably, the active centers are octahedral cobalt ions. Thus, the obtained magnetic nanoparticles can be used for the adsorptive removal of pollutants, catalytic decomposition of the H2O2 and low-frequency hyperthermia.

Optimization of TiO2-P25 photocatalyst dose and H2O2 concentration for advanced photo-oxidation using smartphone-based colorimetry.

Color images taken by a smartphone camera were used to estimate the rate of advanced photo-oxidation reaction of Direct Red 23 (DR23) azo dye as a model organic pollutant. The red, green, blue color coordinates were tested to quantify the dye. Images of the reaction mixture were taken at specified intervals to obtain kinetic lines and reaction rate constants. Both the reaction rate constant and the final degree of degradation were plotted as functions of the photocatalyst dose and the concentration of H2O2. The smartphone measurements are fully consistent with the reference spectrophotometry data. The maximum degradation efficiency of the DR23 dye was recorded at C0(H2O2) = 2.5 mM and photocatalyst dose equal to 1.0 mg/L. Higher H2O2 concentrations reduce the degradation rate as a result of the side reaction of H2O2 with OH radicals. A two-factor experimental design was used to study the effects of photocatalyst dose and H2O2 concentration with five and seven levels, respectively. The analysis of variance results indicated that the concentration of H2O2 had the greater influence. The smartphone provides quick and easy measurement of the photodegradation rate directly in the solutions without sampling. The proposed approach can be applied under field conditions in wastewater treatment plants.

Determination of SLES in Personal Care Products by Colloid Titration with Light Reflection Measurements.

The method of colloid titration with poly(diallyldimethylammonium) chloride has been improved to detect the endpoint with an off-vessel light reflectance sensor. The digital color sensor used measures light reflectance by means of light guides, with no immersion into the reaction solution. In such a method, the optical signal is free of disturbances caused by sticky flocs in the solution. The improved automatic titration set was applied for the determination of sodium laureth sulfate (SLES) in industrial batches and commercial personal care products. The sample color and opacity do not disturb the SLES quantification. When the SLES content lies in the range from 5% to 9%, the optimal sample weight is from 6 g to 3 g.

Magnesium-zinc ferrites as magnetic adsorbents for Cr(VI) and Ni(II) ions removal: Cation distribution and antistructure modeling.

The magnesium-zinc ferrites Mg1-xZnxFe2O4 (x = 0…1) were studied as magnetic sorbents for environmental applications. Low-temperature Mössbauer spectroscopy was used to determine the distribution of magnesium and ferric ions in the spinel crystal lattice. The influence of Zn content on magnetic parameters was investigated on the basis of VSM data. As the molar ratio of zinc to magnesium increases from 0 to 1, the pHPZC value decreases from 10.5 to 8.9. Langmuir and Freundlich models were used to check whether single-layer or multi-layer adsorption occurs. The adsorption of Cr(VI) and Ni(II) ions is well fitted by the Langmuir equation. To check the physical or chemical nature of the sorption process, the Dubinin-Radushkevich equation was used. It was found that the processes of adsorption of Cr(VI) and Ni(II) ions are of a chemical nature. The best Cr(VI) ion adsorption capacity was found for the Mg0·2Zn0·8Fe2O4 sample (qe = 30.49 mg/g). The percentage of heavy metal removal by the mixed ferrite samples increases with increasing zinc content. The most effective sorbent for Ni(II) removal is the Mg0·4Zn0·6Fe2O4 sample (93.2%). Modeling the antistructure provides deeper insight into the mechanism of heavy metal adsorption. The obtained magnesium-zinc ferrites are promising magnetic adsorbents for removing chromate and nickel ions from the environment.

Carrageenan as a functional additive in the production of cheese and cheese-like products.

Carrageenan is a well-known gelling agent used in the food industry. The present review of patent and scien- tific literature shows that carrageenan is a useful additive in the cheese production process. The gel-strength- ening properties of carrageenan are as a result of the fairly strong bonds it forms with casein macromolecules. However, carrageenan-casein interaction is dependent on pH. Different carrageenan types have different charge levels (the most charged is the helix form of lambda-carrageenan), which affects the carrageenan- casein aggregates. The correct concentration of carrageenan and temperature treatment can improve cheese yield and whey protein recovery, which is desirable for cheese producers. Even small amounts of this hydro- colloid can increase cheese firmness and maintain cheese structure after cheese curd heating. Carrageenan improves cheese structure and other properties, such as ease of grating or slicing, which are very important for customers. Some modifications to cheese composition can destroy the natural cheese structure, but the addition of carrageenan can be useful for creating modified cheese-like products with desirable attributes. Carrageenan can be a good replacement for emulsifying salts, to stabilize cheese fat without disturbing the Ca:P ratio. The replacement of emulsifying salts with carrageenan (as little as 1%) results in a homogenous cheese product. For that reason, carrageenan is a useful additive for maintaining the organoleptic and struc- tural values of fat-free cheese. Carrageenan can also stabilize the structure in cheese-like products and replace casein in cheese imitations.

Determination of carrageenan by means of photometric titration with Methylene Blue and Toluidine Blue dyes.

A new approach to carrageenan quantitation was described. The method consists in titration of carrageenan solution by Methylene Blue dye or Toluidine Blue dye solution until a certain absorbance value. The optimal wavelengths are 660nm and 640nm when titrating with Methylene Blue dye and Toluidine Blue dye, respectively. Rectilinear calibration plots (R2>0.996) provide carrageenan determination in the concentration range from 2 to 60mg/L with relative standard deviation from 1 to 5%. The proposed method is simple and feasible in use due to optical dip probe providing in situ absorbance measurements. The proposed way of end-point recognition as pre-set voltage is applicable with any automatic titrator. The method was tested on model jelly dessert sachet. No interference was registered from typical ingredients of jellies such as sucrose, citric acid, sodium citrate, malic acid, potassium sorbate as well as blue colorant. The neutral polysaccharides such as guar gum and locust bean gum have insignificant interference when their content is fivefold as compared to that of carrageenan.

Determination of Poly(Diallyldimethylammonium Chloride) via Spectrophotometric Titration with Coomassie Brilliant Blue G Dye.

Poly(diallyldimethylammonium chloride) (PDDA) is used as organic coagulant in water purification and auxiliary agent in paper production. Determination of PDDA in aqueous solutions is carried out usually by means of polyelectrolyte titration using streaming current detector or o-Toluidine Blue dye for endpoint recognition. The proposed method of PDDA assay takes advantage of Coomassie Brilliant Blue G dye having strong affinity to cationic macromolecules. Titration of PDDA solution with the dye is carried out measuring absorbance at 585 nm. Inflection points of the obtained zigzag photometric curves have good repeatability provided that titration rate is low enough to attain endpoint for 1 hour or more. The method assures rectilinear calibration (R² = 0.999 5) in the broad range of PDDA concentrations from 0.3 to 9.6 mg · dm⁻³.

Assessment of both environmental cytotoxicity and trace metal pollution using Populus simonii Carr. as a bioindicator.

The level of environmental pollution in the city of Ivano-Frankivsk (Western Ukraine) has been assessed by means of roadside poplar trees as bioindicators. Dividable apical meristem cells of rudimentary leaves were quantitatively analysed for mitotic activity and distribution. Anaphases were further examined for chromosomal aberrations. Male catkins were also examined for sterile pollens. Accumulation of trace elements in vegetative buds was also evaluated in order to reveal source(s) of environmental pollution. Poplar trees growing in the urban environment proved to have increased chromosomal aberrations (up to 4-fold) and increased pollen sterility (up to 4-fold) as well as decreased mitotic activity (by factor 1.5) as compared to control sampling site. The biomarker data correlate moderately with increased (up to 4-fold) concentrations of Ni, Zn, Pb, Cd and Cu in vegetative tissues suggesting that probable cause of the environmental cytotoxicity may be vehicle emissions. The maximum increase in chromosomal aberrations (7-fold) and the minimum mitotic activity (half of the control one) were recorded in poplar trees growing in industrial suburb in vicinity of large cement production plant. Taking in mind insignificant bioaccumulation of trace elements in the industrial suburb, the high environmental toxicity has been ascribed to contamination in cement and asbestos particulates.