Modelling non-homogeneous flow and residence time distribution in a single-screw extruder by means of Markov chains

Non-homogeneous velocity distribution of the flow in the channel of a single-screw extruder is taken into account by a new model developed on the basis of the Markov chains. This model allows calculating the Residence Time Distribution (RTD) as well as the influence of the operating conditions on the process at any velocity distribution in the channel. It has been used to represent experimental results on mass flow rate and RTD previously obtained by extrusion of an acrylic polymer, Eudragit E100, at different temperatures and screw rotation speeds. The diffusion coefficient is the only adjusting parameter of the model. It was shown that it does not depend on the screw rotation speed and a correlation between this diffusion coefficient and the barrel temperature was found. The model provides global understanding of the transport kinetics of the flowing material through the extruder according to its behaviour and better describes the progress of the polymer flow all along the barrel from the hopper to the die.     

On-line purge and trap gas chromatography for monitoring of trihalomethanes in drinking water distribution systems

A method using an automated on-line purge and trap gas chromatograph with a dry electrolytic conductivity detector (DELCD) has been developed for monitoring four regulated trihalomethanes in drinking water distribution systems. This analyzer samples trihalomethanes from drinking water by pervaporation through a silicone capillary membrane contained within a gas extraction cell (GEC) followed by preconcentration using an adsorbent trap. Trihalomethanes are subsequently desorbed from the trap onto a capillary column, separated and detected. The analyzer operates in real-time, samples directly from the drinking water distribution system and is fully automated. The optimization, operation, and evaluation of the analyzer and method are discussed. Method detection limits (MDL) are less than 1.0 μg L⁻¹ with acceptable estimates for accuracy, and precision. The results from two on-line monitoring studies in chlorinated and chloraminated distribution systems are presented. The performance of the method is compared directly to United Stated Environmental Protection Agency Method 502.2 and shows a very slight, but acceptable bias.     

On-line monitoring of trihalomethane concentrations in drinking water distribution systems using capillary membrane sampling-gas chromatography

Trihalomethane concentrations are not typically monitored continuously in drinking water distribution systems. This means that data is not immediately available to operators so that they can make decisions that directly affect water quality. Monitoring data could be useful to researchers and operators who might want to better understand disinfection by-product formation and removal in their distribution systems. In this paper, a capillary membrane sampler (CMS), which uses a silicone membrane to directly sample trihalomethanes from a water sample, shows promise as a sampling device that can be used to introduce samples directly into a gas chromatograph for on-line monitoring. The construction, optimization, operation and evaluation of this capillary membrane sampling-gas chromatograph (CMS-GC) are discussed. The result of optimization, method detection limit, accuracy, precision and linearity studies are presented. Side-by-side studies have been done comparing the CMS-GC method to USEPA Method 502.2. While the CMS-GC method is not meant to replace USEPA Method 502.2, it does offer advantages for on-line monitoring and meets several of the criteria proposed as desirable for on-line monitoring of THM concentrations in drinking water distribution systems.     

On-line photo-derivatization with flow injection and liquid chromatography-atmospheric pressure electrospray mass spectrometry for the identification of indoles

The application of on-line photochemistry with flow injection (FI) and liquid chromatography (LC) in conjunction with atmospheric pressure electrospray mass spectrometry (LC-APESI-MS) for the identification of similar indole derivatives is reported here. The photo-transformation of the indole compounds is strongly affected by the substituent groups on the aromatic and heterocyclic rings. Upon photolysis for 2.5 min, the mass spectrum of tryptamine (Try) which has no OH substituent on the aromatic ring does not differ greatly from that obtained without photolysis. However, after photolysis of serotonin (Ser) which has one OH group on C5 of the aromatic ring, the mass spectrum indicates the formation of dimers and higher molecular weight ions. The fragmentation pattern of 5-hydroxytryptophol (Phol) without photolysis resembles that of Ser with a base peak of m/z 160. Upon photolysis using MeOH-H₂O (10/90), Phol is found to form a base peak at m/z 375 (100%) and a major peak at m/z 214 (66%) in addition to other ions with lower abundance. Melatonin (Mel) and tryptophan (Phan) upon photolysis are found to form high molecular weight ions with a relative low abundance. The mass spectrum of indole-3-acetic acid (Inaa) with on-line photolysis also shows different ions that are not formed without photolysis.     

On-line ion-exchange preconcentration in a flow injection system coupled to capillary electrophoresis for the direct determination of UV absorbing anions

On-line ion-exchange preconcentration, performed in a flow injection analysis system, has been integrated with capillary electrophoresis via a specially designed interface, and a sensitive and selective method for the determination of nitrite, nitrate, bromide and iodide using direct UV absorbance detection has been developed. Fivefold enrichment of these aforementioned anions can be realised. Separation conditions such as carrier electrolyte and concentration of electroosmotic modifier were investigated. Limits of detection were ca. 10 ng ml⁻¹ for nitrite and nitrate in aqueous samples, and the overall relative standard deviation was about 5%.     

On-line simultaneous monitoring of glucose and acetate with FIA during high cell density fermentation of recombinant E. coli

A two-channel flow injection analysis (FIA) system was developed for the simultaneous on-line monitoring of acetate and glucose during high cell density fed-batch fermentations of recombinant Escherichia coli. Acetate measurement was performed with a modified and optimised version of an existing method, based on acetate diffusion through a gas-diffusion chamber into a stream containing an acid-base indicator. The subsequent decrease in the absorbance was detected with an incorporated photometer. After method optimisation, it was possible to achieve linearity until 10 g/kg with no dilution step and with a detection level of 0.05 g/kg. Although some interferences were found, the performance of the method proved to be sufficiently reliable for on-line control purposes Commercially packed glucose oxidase (GOD) was used for the amperometric measurement of glucose. The method was linear up to 5 g/kg and it was possible to detect concentrations lower than 0.06 g/kg. For these measurements, no significant interferences were detected when the results were compared with other reference methods. The application of a simultaneous parallel configuration of the methods to a high cell density fed-batch E. coli fermentation was tested and reliable results were obtained within a 3 min delay. This information was made available to a supervisory computer running a developed LabVIEW™ programme via an Ethernet network, allowing the immediate implementation of control actions, improving the process performance.     

On-line galvanic cell generated electrochemiluminescence determination of acyclovir based on the flow injection sampling

A new simple, rapid and cost effective flow injection (FI) electrochemiluminescence (ECL) method was described for the determination of acyclovir (9,2-hydroxyethoxy) methyl guanine. In the presence of acyclovir, the luminol electrochemiluminescence generated by a mini on-line galvanic cell could be greatly sensitized in alkaline medium. The relative electrochemiluminescence intensity was found to increase linearly with increasing concentration of acyclovir, which was corroborated by the calculated correlation coefficient value of 0.9994 (n=7). The limit of detection was 1.6×10⁻⁷ mol l⁻¹ and the limit of quantification was 7.9×10⁻⁷ mol l⁻¹. The proposed method was applied to the determination of acyclovir in pharmaceutical formulations. The reliability of the assay method was established by parallel determination and by standard-addition method. Experiment results demonstrated the described mini analysis system, while being simple and less time consuming, was accurate, precise and reproducible (R.S.D. = 1.6%, recoveries = 99 - 103%). Further experiments indicated that there was no significant difference between the results obtained by the proposed and official methods.     

On-line monitoring of composite nanoparticles synthesized in a pre-industrial laser pyrolysis reactor using Laser-Induced Breakdown Spectroscopy

Laser-Induced Breakdown Spectroscopy (LIBS) was employed for on-line and real time process monitoring during nanoparticle production by laser pyrolysis. Laser pyrolysis has proved to be a reliable and versatile method for nanoparticle production. However, an on-line and real time monitoring system could greatly enhance the process optimization and accordingly improve its performances. For this purpose, experiments aiming at demonstrating the feasibility of an on-line monitoring system for silicon carbide nanoparticle production using the LIBS technique were carried out. Nanosecond laser pulses were focused into a cell through which part of the nanoparticle flux diverted from the production process was flowed for LIBS analysis purposes. The nanoparticles were vaporized within the laser-induced plasma created in argon used as background gas in the process. Temporally-resolved emission spectroscopy measurements were performed in order to monitor nanoparticle stoichiometry. Promising results were obtained and on-line Si/C_x stoichiometry was successfully observed. These results put forward the possibility of real time correction of the nanoparticle stoichiometry during the production process.     

On-line HPLC combined with multivariate statistical process control for the monitoring of reactions

On-line high performance liquid chromatography is used to monitor a steady state reaction over 35.2 h, with 197 chromatograms recorded as the reaction progresses. For each chromatogram, peaks are detected, baseline corrected, aligned and integrated to provide a peak table consisting of the intensities of 19 peaks, two corresponding to the reactants, one to the product and one to the solvent, the remaining being impurities, by-products or intermediates. D-charts and Q-charts from multivariate statistical process control are applied to the data to determine which samples are out of control and also provide diagnostic insight into why these samples are problematic. The D-chart is best at looking at overall performance issues such as problems with mixing or difficulties with instrument operation, whereas the Q-charts are best at detecting impurities during the reaction.     

Modeling the effects of column packing quality and residence time changes on protein monomer/aggregate separation

The packing quality of chromatography columns used for the purification of protein therapeutics is routinely monitored to ensure consistent and reproducible performance. In this work, we used established chromatography models to determine the effect of column packing quality and fluid residence time on the separation of protein therapeutic monomer and aggregate species using a hydrophobic interaction chromatography adsorbent (Phenyl Sepharose Fast Flow). The relationship between the number of theoretical plates, fluid residence time, and column separation performance was quantified using modeling simulations. The simulations showed the separation depended on both the fluid residence time and the number of theoretical plates. However, when the number of theoretical plates was increased to ≥150, the simulations predicted that the separation performance of the column was not significantly improved. The approach described here could be used as a method to quantify acceptable height equivalent of a theoretical plate values for columns, and serve as a tool to understand how column packing quality impacts a given chromatographic separation prior to column scale-up, as well as during the monitoring of column lifetime in the manufacturing of large scale protein therapeutics.     

On-line, real time monitoring of exhaled trace gases by SIFT-MS in the perioperative setting: a feasibility study

A study is described of the first on line, real time analyses of the exhaled breath of five anaesthetized patients during the complete perioperative periods of laparoscopic surgery. These breath analyses were achieved using a selected ion flow tube, SIFT-MS, instrument, located in the operating theatre at an acceptable distance from the operating table, and coupled to the endotracheal tube in the ventilation circuit via a 5 metre long capillary tube. Thus, inhalation/exhalation breathing cycles, set to be at a frequency of 10 per minute, were sampled continuously for water vapour, the metabolites acetone and isoprene and the propofol used to induce anaesthesia for each operating period that ranged from 20 min (shortest) to 80 min (longest). Whilst there was some loss of water vapour along the long sampling line, the concentrations of the other trace compounds were not diminished. The breath acetone was essentially at a constant level for each patient, but increased somewhat over the longest operating period due to the onset of lipolysis. Most interesting is the clear increase of breath isoprene following abdomen inflation with carbon dioxide. The vapour of the intravenously injected propofol was detected in the exhaled breath and remained essentially constant during the perioperative period. These analyses were performed totally non-invasively and the data were immediately and constantly available to the anaesthetist and surgeon. Exploitation of this development could influence decision making and potentially improve patient safety within the perioperative setting.     

Development of flow injection potentiometric methods for the off-line and on-line determination of fluoride to monitor the biodegradation of a monofluorophenol in two bioreactors

Water treatment has become a source of concern as new pollutants and higher volumes of waste water must be treated. Emerging biological approaches, namely the use of bioreactors, for cleaning processes have been introduced. The use of bioreactors requires the development of efficient monitoring tools, preferably with real-time measurements. In this work, a couple of flow injection systems were developed and optimized for the potentiometric determination of fluoride to monitor a rotating biological contactor (RBC) bioreactor and a sequencing batch reactor (SBR) with off-line and on-line sampling. Both the RBC and the SBR bioreactors were set up for the biodegradation of the halogenated organic compound 2-fluorophenol and, as fluoride was a degradation byproduct, the process was monitored by following up its concentration.The described flow injection potentiometric methods enabled the fluoride determination within the required quantification range 0.10-100 mM. The possible interferences from the growth medium were minimized in-line. The determination rate was 78 h⁻¹ for the off-line monitoring of RBC and 50⁻¹ h for the on-line monitoring of the SBR, with a sample consumption of 0.500 mL and 0.133 mL per determination, respectively. Furthermore, the overall reagent consumption was quite low. The accuracy of the system was evaluated by comparison with a batch procedure. The SBR efficiency was monitored both on-line by the flow system and off-line by HPLC, for comparison purposes.     

On-line dilution and determination of the amount of concentrated hydrochloric acid in the final products from a hydrochloric acid production plant using a sequential injection titration system

An on-line sequential injection titration system for the determination of the concentration of concentrated hydrochloric acid as final product from a hydrochloric acid production plant is described. The system involves on-line dilution of the concentrated hydrochloric acid solution to an acceptable range for direct measurement by merging the sample stream with a de-ionized water diluent stream, followed by mixing in a dilution coil, before aspiration into the sequential injection system. Concentrated standard solutions were treated in exactly the same way as the samples. The system was evaluated for reproducibility, linearity, accuracy, and sample throughput. A linear relationship between peak width and logarithm of acid concentration was found in the range 5.934–8.995 mol l⁻¹ and a concentration of 0.005 mol l⁻¹ NaOH solution was used as titrant. Samples from the production plant showed excellent agreement when compared with the manual and automated batchwise titrations. The relative standard deviation was found to be less than 0.4% with a sample frequency of 30 samples per hour.     

On-line coupling of macroporous resin column chromatography with direct analysis in real time mass spectrometry utilizing a surface flowing mode sample holder

A surface flowing mode sample holder was designed as an alternative sampling strategy for direct analysis in real time mass spectrometry (DART-MS). With the sample holder, the on-line coupling of macroporous resin column chromatography with DART-MS was explored and the new system was employed to monitor the column chromatography elution process of Panax notoginseng. The effluent from macroporous resin column was first diluted and mixed with a derivatization reagent on-line, and the mixture was then directly transferred into the ionization region of DART-MS by the sample holder. Notoginsenosides were methylated and ionized in a metastable helium gas stream, and was introduced into MS for detection. The on-line system showed reasonable repeatability with a relative standard deviation of 12.3% for the peak area. Three notoginsenosides, i.e. notoginsenoside R₁, ginsenoside Rb₁ and ginsenoside Rg₁, were simultaneously determined during the eluting process. The alteration of the chemical composition in the effluent was accurately identified in 9 min, agreeing well with the off-line analysis. The presented technique is more convenient compared to the traditional UPLC method. These results suggest that the surface flowing mode DART-MS has a good potential for the on-line process monitoring in the pharmaceutical industry.     

Flow injection spectrophotometry coupled with a crushed barium sulfate reactor column for the determination of sulfate ion in water samples

A new type of a reactor column, a crushed BaSO₄ reactor column used for the flow injection spectrophotometric determination of sulfate ion using the exchange reaction of sulfate ion and barium-dimethylsulfonazo III is proposed. The column is very simple and economical. It can be continuously used for 8 h before washing with water for repeated usage of at least 1 month. The procedure is sensitive. Application to various water samples was demonstrated.     

On-line trace enrichment of phenolic compounds from water using a pyrrole-based polymer as the solid-phase extraction sorbent coupled with high-performance liquid chromatography

A pyrrole-based conductive polymer was prepared and applied as new sorbent for on-line solid-phase extraction (SPE) of phenol and chlorophenols from water samples. Polypyrrole (PPy) was synthesized by chemical oxidation of the monomer in non-aqueous solution. The efficiency of this polymer for extraction of phenol and chlorophenols was evaluated using 35 mg of PPy as the sorbent in an on-line SPE system coupled to reversed-phase liquid chromatography with UV detection. The mobile phase were mixture of phosphate buffer-acetonitrile and compounds were eluted by the mobile phase using a six-port switching valve. High volumes of water, up to 160 ml, could be preconcentrated without the loss of phenols, except for the more polar ones. The R.S.D. for a river water sample spiked with phenol and chlorophenols at sub-ppb level was lower than 7% (n=5) and detection limits of 15-100 and 35-150 ng l⁻¹ for tap and river water were obtained, respectively.     

On-line sorption preconcentration of metals based on mixed micelle cloud point extraction prior to their determination with micellar chemiluminescence: Application to the determination of chromium at ng l levels

The on-line incorporation of cloud point extraction (CPE) to flow injection analysis (FIA) is modified to extract and preconcentrate metal species rapidly, avoiding the formation of hydrophobic complexes, using a mixed micellar medium. Coupling the procedure with chemiluminescence (CL) detection based on the catalytic activity of metal species on the luminol-hydrogen peroxide reaction and enhancing the signal with the presence of a micellar carrier containing bromide ions produces a powerful tool for the preconcentration and determination of metal species at ng l⁻¹ levels. As an analytical demonstration ultratrace concentrations of chromium were conveniently detected and quantified in samples with a complex matrix such as seawater and wastewater. The figures of merit for the determination of chromium were: 0.9-1.6% R.S.D. (n=5) with detection and quantification limits 0.5 and 2.0 ng l⁻¹, respectively. The calibration graph was rectilinear from 2 to 200 ng l⁻¹ (r=0.9996, n=6). Several other metal ions were determined in ideal situations, with analogous results.     

A simple strategy for determining ethanol in all types of alcoholic beverages based on its on-line liquid-liquid extraction with chloroform, using a flow injection system and Fourier transform infrared spectrometric detection in the mid-IR

In this work, a simple strategy for the determination of ethanol in all types of alcoholic beverages using Fourier transform infrared spectrometric detection has been developed. The methodological proposal includes the quantitative on-line liquid-liquid extraction of ethanol with chloroform, through a sandwich type cell equipped with a PTFE membrane, using a two-channel manifold; and direct measurement of the analyte in the organic phase, by means of Fourier transform infrared spectrometry. The quantification was carried out measuring the ethanol absorbance at 877 cm⁻¹_, corrected by means of a baseline established between 844 and 929 cm⁻¹. The procedure, which does not require any sample pretreatment (except for the simple degassing of beer and gassy wine samples, and a simple dilution of spirits with water), was applied to determine ethanol in different alcoholic beverages such as beers, wines and spirits. The results obtained highly agree with those obtained by a derivative FTIR spectrometric procedure, and by head space-gas chromatography with FID detection. The proposed method is simple, fast, precise and accurate. Moreover, it can be easily adapted to any infrared spectrometer equipped with a standard transmission IR cell, and provides attractive analytical features, which are comparable to, or better than those offered by other published methods. In consequence, it represents a valid alternative for the determination of ethanol in alcoholic beverages, and could be suitable for the routine control analysis.     

Monitoring polyolefin modification along the axis of a twin‐screw extruder. II. Maleic anhydride grafting

The physico‐chemical phenomena developing along the screw axis of a twin‐screw extruder during the grafting of maleic anhydride (MA) onto polyolefins [polyethylene (PE), ethylene–propylene rubber (EPM), and polypropylene (PP)] were investigated. For this purpose, sampling devices located along the extruder barrel were used to collect polymer samples that were subsequently characterized to follow the degrees of grafting and crosslinking or degradation. A similar evolution of MA grafting was observed regardless of the polyolefin type or MA and peroxide concentration when grafting was performed under identical conditions, that is, the same peroxide type and set temperature. A correlation between the MA grafting and the calculated peroxide decomposition was established. Chemical reactions occurred along the extruder axis until the peroxide was fully converted. More detailed quantitative measurements of the peroxide decomposition and MA grafting would allow the development of accurate process models. The final MA content depended on the polyolefin composition (PE > EPM ≫ PP). As expected for PE, crosslinking occurred in addition to grafting, but after a certain residence time, the PE network degraded. The PP viscosity reduction after MA grafting was due to the conversion of tertiary PP radicals into primary PP radicals after grafting. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 3919–3932, 2000