Fabrication of a Smart Nanofluidic Biosensor through a Reversible Covalent Bond Strategy for High-Efficiency Bisulfite Sensing and Removal.

Bioinspired nanochannel based biosensors have been widely applied for sensing ions, small molecules, and biomolecules. However, the low selectivity and difficulty in recycle sensing still heavily hamper their widespread applications. Herein, we designed and fabricated a nanochannel based biosensor for high-efficiency bisulfite (HSO3-) sensing and removal through forming a reversible covalent bond between HSO3- and 4-aminophenyl-phenyl-methanone (APPM). This nanofluidic biosensor displays a promising HSO3- selectivity with high ion rectification/gating ratio (47 and 5) and excellent reversibility and stability. Of note, the L02 cell line containing excess HSO3- could still maintain high vitality in the presence of such an APPM-functionalized biosensor based membrane. These results will not only help to better understand the biological function of HSO3- in living organisms but also inspire us to develop smart artificial nanochannel based biosensors for biological applications.

Novel pararosaniline based optical sensor for the determination of sulfite in food extracts.

Sulfite, which is a protective agent in various food industries, also is known as an allergen. Therefore, sulfite content in food must be monitored and controlled. In this context, a novel optical sensor is designed for simple, rapid and sensitive determination of the sulfite content in food samples. Acidified pararosaniline (PRA) hydrochloride reagent in cationic form was immobilized on the surface of the Nafion cation exchanger membrane by electrostatic interactions. In formaldehyde medium, the pale purple PRA-Nafion film was converted to rich purple due to the highly conjugated alkyl amino sulfonic acid formation in the presence of sulfite and the absorbance change at 588 nm was recorded. The proposed optical sensor gave a linear response in a wide concentration range for sulfite. The limit of detection (LOD) and the limit of quantification (LOQ) values obtained for sulfite were 0.084 and 0.280 ppm SO2 equivalent, respectively. The proposed optical sensor was validated in terms of linearity, additivity, precision and recovery parameters. The sulfite contents obtained for real food extracts were found to be comparable to the conventional iodometric titration results (with the exception of highly colored samples containing reducing agents, where iodometry was shown to exhibit a systematic error while the proposed sensor could measure the true value). The proposed optical sensor is insensitive to positive interferences from turbidity and colored components of the sample. Sulfite determination in a complex food matrix can be performed using the rapid, simple and sensitive PRA-based sensor without a need for pre-treatment.

A simple field method for the determination of sulfite in natural waters: Based on automated dispersive liquid-liquid microextraction coupled with ultraviolet-visible spectrophotometry.

Sulfite is known to be harmful to human health and associated to sulfur related environmental effects and ideally should be analyzed onsite owing to its instability. Here we describe an automated, miniaturized, and highly efficient dispersive liquid-liquid microextraction (DLLME) system that seamlessly coupled to a UV-vis spectrophotometer for the trace analysis of sulfite in natural waters. The automated DLLME system was constructed by a single syringe pump that is coupled with a multiposition valve. Nanomolar levels of sulfite could be extracted from natural water samples and injected into the hyphenated spectrophotometer for quantification. The whole analytical procedures, including chromogenic reactions, DLLME, collecting and transferring of microvolume of extracts, and spectrophotometric quantification, were automatically carried out. Key parameters that affect the performance of the method were investigated. The method allows the determination of trace levels of sulfite in the range of 15-1500 nM with a detection limit of 1.2 nM. Good reproducibility and recoveries were obtained by analyzing a series of natural water samples that were spiked with different concentration levels. The method was successfully applied to real natural water samples with satisfactory results. The proposed analytical system is light (3.9 kg), simple to use, able to be applied in the field, and sensitive enough for fresh and saline waters analysis.

Determination of free and total sulfur(IV) compounds in coconut water using high-resolution continuum source molecular absorption spectrometry in gas phase.

This work proposes a method for the determination of free and total sulfur(IV) compounds in coconut water samples, using the high-resolution continuum source molecular absorption spectrometry. It is based on the measurement of the absorbance signal of the SO2 gas generate, which is resultant of the addition of hydrochloric acid solution on the sample containing the sulfating agent. The sulfite bound to the organic compounds is released by the addition of sodium hydroxide solution, before the generation of the SO2 gas. The optimization step was performed using multivariate methodology involving volume, concentration and flow rate of hydrochloric acid. This method was established by the sum of the absorbances obtained in the three lines of molecular absorption of the SO2 gas. This strategy allowed a procedure for the determination of sulfite with limits of detection and quantification of 0.36 and 1.21mgL-1 (for a sample volume of 10mL) and precision expressed as relative standard deviation of 5.4% and 6.4% for a coconut water sample containing 38.13 and 54.58mgL-1 of free and total sulfite, respectively. The method was applied for analyzing five coconut water samples from Salvador city, Brazil. The average contents varied from 13.0 to 55.4mgL-1 for free sulfite and from 24.7 to 66.9mgL-1 for total sulfur(IV) compounds. The samples were also analyzed employing the Ripper´s procedure, which is a reference method for the quantification of this additive. A statistical test at 95% confidence level demonstrated that there is no significant difference between the results obtained by the two methods.

[Performance of cross flow trickling filter for H2S gas treatment].

A grading cross bio-trickling filter was designed for H2S removal. Mixed microorganisms domesticated from the former experiment were immobilized to start up the trickling filter. Removal performances during starting up period and different loadings were investigated. Results showed that the immobilization of the trickling filter was completed within 3 d. The removal efficiency was higher than 99% when the inlet concentration was in the range of 110 mg x m(-3) to 230 mg x m(-3) (EBRT 30 s). At low inlet loadings, the front part of the trickling filter played a major role in H2S degradation, accounting for about 85%. Microbial diversity and population of the front part were superior to the tail one. At higher loadings, microbial diversity and population of the tail part increased significantly, from 4.5 x 10(7) cells x g (-1) to 5.17 x 10(8) cells x g(-1), and the elimination capacity was also improved,from 0.04 g x h(-1) to 0.67 g x h(-1). Rod-shaped bacteria were the dominant microorganisms on the surface of ceramics in the steady state as observed by SEM. The surfaces of ceramics were covered by a lot of microbial metabolites at high loadings. Analysis of the metabolites indicated that the majority of H2S was oxidized to sulfur and only a small portion was converted to sulfate.

The effects of nutrient limitation (nitrogen and phosphorus) on BOD removal from post-coagulated Pinus radiata sulfite pulp and paper mill wastewater in a baffled aerated stabilisation basin-laboratory pilot scale study.

The use of coagulation and flocculation for tertiary treatment of pulp and paper mill effluent was investigated, where the evaluation was based on the removal of nitrogen (N), phosphorus (P) and BOD from post-coagulated wastewater. The study was undertaken on laboratory scale aerobic stabilisation basins (ASB). Two post coagulated (alum) wastewaters were studied, where the BOD:N:P ratios were 100:1.3:0.06 and 100:1.3:0.3. These wastewaters were treated in two identical concurrent simulations (A & B). The influent ratio for 'A' was selected representing the composition of actual coagulated Pinus radiata sulfite pulp effluent mixed with paper mill effluent. The input composition for 'B' represented a typical P concentration found in existing pulp and paper mill effluents. Unmodified sludge collected from a mill-pond was added at 4% v/v to each simulation replicating the treatment conditions at full-scale. Similar high percentage removals of BOD and COD occurred after 28 days (two HRTs) which were 94 and 67% respectively for 'A', and 98 and 70% respectively for 'B', where both remained at steady state during the third HRT. A statistical analysis of the data revealed that there was no significant difference in the sample variance of the BOD and COD results.

Molasses as an external carbon source for anaerobic treatment of sulphite evaporator condensate.

Failures in stability and COD removal performance often occurred in full-scale anaerobic reactors treating the evaporator condensate from a sulphite pulp mill due to substrate inhibition and occasional contaminations with red liquor (wood cooking liquor). With this work, the beneficial effect provided by the continuous addition of an external carbon source (sugarcane molasses) on the overall performance and stability of the biological process was evaluated. With a moderate addition of molasses the inhibition was mitigated which led to an increase of the COD removal rate from 52% to 77% and a methane production increase from 460 to 1650mld(-1) at an organic loading rate of 2.61g CODl(-1)d(-1). A similar conclusion can be drawn for the case when contamination with red liquor occurs. These results suggest that sugarcane molasses addition may be regarded as a low-cost operational strategy for the anaerobic treatment of sulphite evaporator condensate.

Dietary intake of sulphites by children in the Slovak Republic.

The mean dietary intake of sulphites by Slovak children aged 7 to 10 years was estimated. Calculations were based on a food model of a specific boarding-school in January, May, July and October while respecting the scientifically recommended dietary allowances. It was assumed that sulphites were used in the widest possible range of foods and at maximum permitted levels. Due to this fact and since sulphites are partially lost during food processing and storage, the results are over-estimated. However the mean daily exposure of consumers with the lowest (21 kg) and the mean (26.5 kg) body weight to sulphites ranged from 44 to 55% and from 36 to 43% of the acceptable daily intake value (ADI) respectively. Due to availability of various foods the dietary models were not affected seasonally and thus no differences among intakes of sulphites in individual months were obvious. The results indicated that the above mentioned group of children is sufficiently protected from the hazard of sulphites in food.

Capillary electrophoretic separation of inorganic sulfur-sulfide, polysulfides, and sulfur-oxygen species.

A CE protocol was developed for the identification and separation of inorganic polysulfides simultaneously with other inorganic sulfur-bearing species coexisting in aqueous hydrosulfide/sulfur solutions. The electrophoretic separation of thiosulfate, sulfate, hydrosulfide, sulfite, tetrathionate, and polysulfides was achieved at pH values between 8.2 and 12.2. The peaks attributed to the polysulfide species were strongly sensitive to pH. CE analysis of hydrosulfide/sulfur solutions at different pH values permitted possible identification of two forms of polysulfides: S4(2-) and S3(2-). Upon exposure to air at ambient temperature, thiosulfate was the main oxidation product of hydrosulfide/sulfur solutions mainly in the first 60 min, when hydrosulfide was rapidly consumed. Analysis of the oxidation reaction products provided retrospectively tentative evidence that the peaks separated and identified as tri- and tetrasulfide may be ascribed to polysulfides.

Removal of sulfide, sulfate and sulfite ions by electro coagulation.

The removal of various species of sulfur from beamhouse of tannery wastewater and also from synthetic samples was studied by electro-flotation technique. Consumable anodes of iron and aluminum and insoluble anode of titanium were tested as anodes. It was found that iron and aluminum anodes were effective for the removal of suspended solids, sulfide, sulfite and sulfate. Progress of simultaneous coagulation of suspended solids during electro-flotation was measured using particle size analysis. Coagulation was found to be essential for effective flotation of suspended solids. Metal ions generated in situ by electrolytic oxidation of anode were found to react with dissolved sulfide ions. Metal sulfides thus formed as colloidal suspension were coagulated and floated simultaneously by hydrogen bubbles generated from cathode. Simultaneous occurrence of precipitation, coagulation and flotation was observed during electro-flotation. X-ray diffraction studies were conducted to identify the nature of sulfide phase formed during electrolytic precipitation. The effect of pH, current density and initial concentration of pollutants was studied and the results are discussed. The removal of sulfite and sulfate ions is explained by zeta-potential measurements.

[Ion chromatography of L-ascorbic acid, sulfite and thiosulfate using their postcolumn reactions with cerium (IV) and fluorescence detection of cerium (III)].

An ion chromatographic method was used to separate the species of L-ascorbic acid, sulfite and thiosulfate in their mixtures. This method is based on the separation of each anion in their mixtures by using a separation column, and then on the fluorimetric measurement of cerium (III) formed by a postcolumn reaction of cerium (IV) with the species of L-ascorbic acid, sulfite and thiosulfate in the effluent. The optimal conditions for separating and determining the above three species have been established. By using a 3 mmol/L carbonate eluent, the species of L-ascorbic acid, sulfite and thiosulfate could be eluted at the proper retention times of 1.7, 2.6 and 5.0 min, respectively, and these three anions could be separated completely. The effects of the concentrations of cerium (IV) and sulfuric acid in the postcolumn reaction solution on the chromatographic peak-height were tested in order to obtain the optimal peak-height. It was found that the peak-height at first increases rapidly with an increase in the concentration of cerium (IV) and sulfuric acid respectively up to a certain concertation, then increases slowly. These critical concentrations of cerium (IV) and sulfuric acid also depend on the amount of the analyte injected. Meanwhile the baseline signals of the sepectra increase with an increase in the concentration of cerium (IV). Some concentrations above the critical concentration of sulfuric acid could be selected as the optimal concentration of sulfuric acid, but the concentration of cerium (IV) should be optimized by establishing a compromise between the higher peak-height and the lower baseline signal. The detection limit of this method was found to be 1 mumol/L for thiosulfate when an amount of 100 microL analyte was injected.

The formation of exchangeable sulphite from adenosine 3'-phosphate 5'-sulphatophosphate in yeast.

A new low-molecular-weight bound sulphite was found in yeast enzyme reaction systems which convert the sulphur of 35S-labelled adenosine 3'-phosphate 5'-sulphatophosphate into exchangeable radioactive sulphite. This bound sulphite was separated from other components by paper electrophoresis and Sephadex G-25 chromatography, and shown to be a peptide with multiple thiol groups and an estimated mol.wt. of 1400. The labelled sulphur in this peptide is highly exchangeable with unlabelled sulphite, but exchangeability decreases with time and freeze-drying. The low-molecular-weight acceptor is tightly bound to enzyme B of the yeast system and, apparently, accepts the sulpho group of adenosine 3'-phosphate 5'-sulphatophosphate and is released as bound sulphite only in the presence of enzymically or chemically reduced fraction C. It is proposed that the low-molecular-weight acceptor is a carrier peptide which, after release of the reduced sulphur, becomes re-oxidized and returns to enzyme B. Fraction C appears to function as an obligatory reductant of the oxidized acceptor before it can accept another-SO-3-moiety from adenosine 3'-phosphate 5'-sulphatophosphate. These findings are consistent with mechanisms proposed for sulphate reduction in spinach and Chlorella, and suggest that fraction C is the natural thiol required in these systems. An improved column technique for the preparation of adenosine 3'-phosphate 5'-sulphatophosphate is described.