Effect of clarification process on the removal of pesticide residues in red wine and comparison with white wine.

The aim of this study was to determine the potential of seven clarifying agents to remove pesticides in red wine. The presence of pesticides in wine consists a great problem for winemakers and therefore, results on pesticide removal by clarification are very useful for taking a decision on the appropriate adsorbent. The selection of an efficient adsorbent can be based on data correlating pesticide removal in red wine to pesticides' properties, given the great number and variety of pesticides used. So, this experimental work is focused on the collection of results with regard to pesticide removal by clarification using a great number of pesticides and fining agents. A Greek red wine, fortified with single solutions and mixtures of 23 or 9 pesticides was studied. The seven fining agents, used at two concentrations, were activated carbon, bentonite, polyvinylpolypyrrolidone (PVPP), gelatin, egg albumin, isinglass-fish glue, and casein. Pesticides were selected with a wide range of properties (octanol-water partition coefficient (log Kow) 2.7-6.3 and water solubility 0.0002-142) and belong to 11 chemical groups. Solid phase extraction (SPE) followed by gas chromatography (GC) with electron capture detector (ECD) were performed to analyze pesticide residues of the clarified fortified wine. The correlation of the clarifying agents' effectiveness to pesticide's chemical structure and properties (log Kow, water solubility) was investigated. The antagonistic and/or synergistic effects, occurring among the pesticides in the mixtures, were calculated by indices. Pesticide removal effectiveness results of the red wine were compared to those obtained from a white wine under the same experimental conditions and discussed. The order of decreasing adsorbent effectiveness (mixture of 23 pesticides) was: activated carbon 40% > gelatin 23% > egg albumin 21% > PVPP 18% > casein 12% > bentonite 7%. Isinglass showed 12% removal at the highest permitted concentration. In the case of 9 pesticides mixture, the effectiveness was quite higher but the order remained the same compared to 23 pesticides mixture. The removal of each pesticide from its single solution was generally the highest (particularly for hydrophobic pesticides). Adsorption on fining agents is increased by increasing hydrophobicity and decreasing hydrophilicity of organic pesticide molecules.

Cupriavidus metallidurans biomineralization ability and its application as a bioconsolidation enhancer for ornamental marble stone.

Bacterially induced calcium carbonate precipitation of a Cupriavidus metallidurans isolate was investigated to develop an environmentally friendly method for restoration and preservation of ornamental stones. Biomineralization performance was carried out in a growth medium via a Design of Experiments (DoE) approach using, as design factors, the temperature, growth medium concentration, and inoculum concentration. The optimum conditions were determined with the aid of consecutive experiments based on response surface methodology (RSM) and were successfully validated thereafter. Statistical analysis can be utilized as a tool for screening bacterial bioprecipitation as it considerably reduced the experimental time and effort needed for bacterial evaluation. Analytical methods provided an insight to the biomineral characteristics, and sonication tests proved that our isolate could create a solid new layer of vaterite on marble substrate withstanding sonication forces. C. metallidurans ACA-DC 4073 provided a compact vaterite layer on the marble substrate with morphological characteristics that assisted in its differentiation. The latter proved valuable during spraying minimum amount of inoculated media on marble substrate under conditions close to an in situ application. A sufficient and clearly distinguishable layer was identified.

Interaction behavior in ultrafiltration of nonionic surfactant micelles by adsorption.

Adsorption of nonionic surfactant micelles onto ultrafiltration (UF), membranes was studied. Two homologous series of nonionic surfactants, namely, Tritons (alkylphenol ethoxylates) and Neodols (alcohol ethoxylates), were used to characterize surface properties of two polymeric ultrafiltration membranes with 20,000 nominal cutoff. Particularly, a cellulose acetate and a polysulfone membrane were investigated. Static adsorption experiments were carried out using surfactant solutions at concentrations above their critical micelle concentration. The characterization of surface properties of UF membranes was based on the adsorption behavior of surfactant species. The adsorption extent on UF membranes was affected by the hydrophobicity-to-hydrophilicity ratio mainly determining the interactions developed at the membrane-surfactant species interface. Adsorption experimental data seem generally to fit the Langmuir isotherm model. Atomic force microscopy was used to examine the alteration of the top membrane surface morphology.

Effect of nonionic surfactants on the solubilization of alachlor.

The ability of nonionic surfactants to solubilize the pesticide alachlor was studied. Two homologue series, octylphenol ethoxylates (Triton X-114, Triton X-100 and Triton X-102) and ethoxylated decyl alcohols (Neodol 91-5E, Neodol 91-6E and Neodol 91-8E) were used at concentrations 3 critical micelle concentration (CMC) and 6 CMC. The rate of solubilization of a sufficient quantity of alachlor (for saturation) in aqueous solution containing the micelles of nonionic surfactant was recorded. The experimental data were fitted to a first-order kinetic model. The rate constant, saturation concentration and enhancement factor were estimated for each surfactant system. The effect of surfactant structure, CMC concentration, pesticide structure and its physicochemical properties on the effectiveness of solubilization was determined. In terms of solubilization capability, the nonionic surfactants of each homologue series can be ranked as follows: Neodol 91-8E>Neodol 91-6E>Neodol 91-5E and Triton X-102>Triton X-100>Triton X-114. The more hydrophilic Neodol series was proved more efficient in alachlor solubilization than Triton series. The enhancement factor values ranged from 1.064 to 1.995 at 3 CMC and 1.320 to 2.919 at 6 CMC. The results will be used mainly for micellar-enhanced ultrafiltration since the extent of solubilization is a critical factor.

Removal of pesticides from white and red wines by microfiltration.

The aim of this work is the investigation of microfiltration in removing pesticides from a white and a red Greek wine. Six membranes with pore size 0.45µm were investigated. Two mixtures of 23 and 9 pesticides, and single pesticide solutions were added in the wine. The pesticides tested belong to 11 chemical groups. Solid phase extraction (SPE) followed by gas chromatography (GC) with electron capture detector (ECD) were performed to analyze pesticide residues of the filtered fortified wine. Distinct behavior was exhibited by each membrane. Cellulose acetate and cellulose nitrate showed higher mean pesticide removal for both wines, followed by polyethersulfone, regenerated cellulose, and polyamides. The filtration effectiveness was correlated to the membrane type and to the pesticide chemical structure and properties (octanol-water partition coefficient, water solubility) and compared for the wines tested. In most cases, the more hydrophobic pesticides (pyrethroids and aldrin) showed higher removal from red wine than white wine. Adsorption on membranes was increased by increasing hydrophobicity and decreasing hydrophilicity of organic pesticide molecule. The removal of each pesticide from its single solution was generally higher than that from its mixtures, allowing the estimation of the antagonistic and synergistic effects of pesticides in the mixtures.

Adsorption of humic acid on acid-activated Greek bentonite.

The adsorption of humic acid on bentonite from Milos Island (Greece) acid-treated with dilute H(2)SO(4) solutions over a concentration range between 0.25 and 13M has been studied. Bentonite activated with 3M sulfuric acid (AAS) showed a higher efficiency in removing humic acid from aqueous solutions and was selected for further investigation. The specific surface area of acid-activated bentonite was estimated using the methylene blue adsorption method. The morphology of untreated, activated, and HA-sorbed bentonite was studied under scanning electron microscope (SEM). The effects of contact time, adsorbate concentration, adsorbent dose, and temperature on the adsorption of humic acid onto bentonite activated with 3M H(2)SO(4) were studied using a batch adsorption technique. Acidic pH and high ionic strength proved to be favorable for the adsorption efficiency. Pseudo-first-order, pseudo-second-order, and intraparticle diffusion models were used to describe the kinetic data and the rate constants were evaluated. The experimental isotherm data were analyzed using Langmuir, Freundlich, and Temkin equations and the isotherm constants were determined. Thermodynamic parameters (DeltaH(o), DeltaS(o), and DeltaG(o)) of adsorption of humic acid onto acid-activated bentonite with 3M sulfuric acid were also evaluated.

Adsorption of pesticides on resins.

The objective of this work was to assess the capability of organic hydrophobic polymeric resins Amberlite XAD-4 and XAD-7 to remove the pesticides alachlor and amitrole from water. The pesticides adsorption on the two different adsorbents was measured by batch equilibrium technique and isotherm types and parameters were estimated. Two theoretical models were applied based on a Freundlich and a Langmuir isotherms. The effect of pesticides chemical composition and structure as well as the nature of solid surface on the efficiency of adsorption was evaluated. The influence of pH also was studied. In low pH solutions adsorption of amitrole was higher upon the nonionic aliphatic acrylic ester copolymer XAD-7 in comparison to the nonionic, crosslinked macroreticular copolymer of styrene divinylbenzene XAD-4. In neutral and intermediate pH solutions the polar acrylic ester copolymer XAD-7 was more effective to the retention of alachlor. The acrylic ester copolymer showed at pH 3 the lower effectiveness in alachlor removal from water. The data of the adsorption isotherms of pesticides upon the examined polymeric resins seemed to conform to both the Freundlich and the Langmuir isotherm models.