Determination of bromate in drinking water by zone electrophoresis-isotachophoresis on a column-coupling chip with conductivity detection

The use of capillary zone electrophoresis (CZE) on-line coupled with isotachophoresis (ITP) sample pretreatment (ITP-CZE) on a poly(methylmethacrylate) chip, provided with two separation channels in the column-coupling (CC) arrangement and on-column conductivity detection sensors, to the determination of bromate in drinking water was investigated. Hydrodynamic and electroosmotic flows of the solution in the separation compartment of the chip were suppressed and electrophoresis was a dominant transport process in the ITP-CZE separations. A high sample load capacity, linked with the use of ITP in this combination, made possible loading of the samples by a 9.2 microL sample injection channel of the chip. In addition, bromate was concentrated by a factor of 10(3) or more in the ITP stage of the separation and, therefore, its transfer to the CZE stage characterized negligible injection dispersion. This, along with a favorable electric conductivity of the carrier electrolyte solution, contributed to a 20 nmol/L (2.5 ppb) limit of detection for bromate in the CZE stage. Sample cleanup, integrated into the ITP stage, effectively complemented such a detection sensitivity and bromate could be quantified in drinking water matrices when its concentration was 80 nmol/L (10 ppb) or slightly less while the concentrations of anionic macroconstituent (chloride, sulfate, nitrate) in the loaded sample corresponding to a 2 mmol/L (70 ppm) concentration of chloride were still tolerable. The samples containing macroconstituents at higher concentrations required appropriate dilutions and, consequently, bromate in these samples could be directly determined only at proportionally higher concentrations.     

Sample decomposition in an electrically heated cold-trap inlet system for high speed gas chromatography

Thermal decomposition of some hydrocarbon and chlorinated hydrocarbon compounds in metal capillary tubes used in an inlet system for high speed gas chromatography has been investigated. The metal tube is cooled to about ?75°C by a flow of cold nitrogen gas in order to focus a vapor sample cryogenically. A capacitive discharge power supply is then used to heat the metal tube resistively in order to revaporize the sample and introduce it to the separation column as a plug 5-10 ms wide. The effects of tube temperature, tube material, sample vapor residence time, and type of carrier gas on thermal cracking are described. Use of a copper-nickel alloy tube resulted in less cracking than either pure platinum or pure nickel. Cracking is more significant with hydrogen as carrier gas than with helium. Cracking also increases with increasing sample residence time in the hot tube. Quantitative sample injection with minimum decomposition can be obtained for a variety of aliphatic and aromatic hydrocarbons and chlorinated hydrocarbon compounds.     

Temperature Modulated Differential Scanning Calorimetry Part IV. Effect of heat transfer on the measurement of heat capacity using quasi-isothermal ADSC

An analysis developed in previous work has been further refined in order to study the effect of heat transfer on the heat capacity and phase angle measurements by TMDSC. In the present model, a temperature gradient within the sample has been taken into account by allowing for heat transfer by thermal conduction within the sample. The influence of the properties of the sensors, the heat transfer conditions between the sensor and sample,and the properties of the sample have been investigated by varying each parameter in turn. The results show that heat capacity measurements are reliable only within a restricted frequency range, for which the experimental conditions are such that the heat transfer phase angle depends linearly on the modulation frequency. This revised version was published online in July 2006 with corrections to the Cover Date.     

Sample evaporation in conventional GC split/splitless injectors. Part 1: Some quantitative estimates concerning heat consumption during evaporation

During sample evaporation in conventional vaporizing injection, the supply of heat to the evaporating liquid is a problem, first because the amounts of heat consumed are relatively large and, secondly, because the heat must be transferred to the sample within a very short time. Times available for evaporation, required amounts of heat, possible sources of heat, and the time required to transfer the heat to the sample liquid are discussed. It is shown that mixing with carrier gas contributes little heat to the evaporation process, but also that packings with glass wool have too low a heat capacity to deliver the required amount of heat to the evaporating sample. Transfer of heat from the insert wall to the sample easily requires several seconds, even if cooling of the vaporizing zone by 20° is accepted. Thus “flash evaporation” is usually impossible and most liquids must be held in the vaporizing chamber to allow full evaporation.     

脉冲加热-红外吸收光谱法测定钒铝合金中氢

对脉冲加热-红外吸收法测定钒铝合金中氢的分析方法进行了研究。通过实验对分析功率、称样量和校正标样等测试条件进行了讨论。实验表明钒铝合金中的氢易释放,对于AlV85样品中氢,热提取法和熔融法测定结果一致;但AlV50样品中氢,热提取法的结果略高于熔融法,故实验中选用热提取法测定钒铝合金中氢量。热提取法用0.75g金属锡作助熔剂,于4.0kW分析功率条件下测定钛标准样品中氢来确定氢工作曲线的校正系数,在1.5kW分析功率下测定钒铝合金中氢,测定结果与高频感应-热导法(用5g钢标准样品对氢的测定进行校正)结果吻合。对3个钒铝合金中氢量进行了测定,结果的相对标准偏差为2.2%～6.5%(n=8)。     

Ti和乳酸共改性α-Fe2O3光阳极光电化学性能研究

采用一步水热后在氮气中进行热处理的方法制备了Ti和乳酸共改性的纳米花状α-Fe₂O₃光阳极。对样品分别进行了X射线衍射、扫描电镜、X射线光电子能谱、紫外-可见吸收光谱和光电化学性能测试。与乳酸改性的纳米片状α-Fe₂O₃光阳极相比,最优的Ti与乳酸共改性样品0.075LA-Fe2O3-0.75Ti光阳极的光电流密度从0.55mA·cm^-2提高到1.39mA·cm^-2。Ti改性明显减少了0.075LA-Fe₂O₃膜的表面态,增加了表面载流子注入效率;同时Ti的掺入也增加了电极体内载流子浓度,增强了体内载流子的传输效率。     

Online Flowing Colloidosomes for Sequential Multi‐analyte High‐Throughput SERS Analysis

3D plasmonic colloidosomes are superior SERS sensors owing to their high sensitivity and excellent tolerance to laser misalignment. Herein, we incorporate plasmonic colloidosomes in a microfluidic channel for online SERS detection. Our method resolves the poor signal reproducibility and inter‐sample contamination in the existing online SERS platforms. Our flow system offers rapid and continuous online detection of 20 samples in less than 5 min with excellent signal reproducibility. The isolated colloidosomes prevent cross‐sample and channel contamination, allowing accurate quantification of samples over a concentration range of five orders of magnitude. Our system demonstrates high‐resolution multiplex detection with fully preserved signal and Raman features of individual analytes in a mixture. High‐throughput multi‐assay analysis is performed, which highlights that our system is capable of rapid identification and quantification of a sequence of samples containing various analytes and concentrations.     

Tandem on-line dialysis with a double and single dialyser in flow injection dialysis — Simultaneous determination of calcium and high chloride in industrial effluents

The on-line double membrane dialyser described previously was coupled in series to a single dialyser in the manifold of a flow injection system to include the determination of samples with a high chloride content simultaneously with calcium in industrial effluents from a single sample injection. 50 μl of industrial effluent samples are injected into a carrier stream and are simultaneously dialysed in the double on-line dialyser for chloride and calcium. The dialysed chloride sample zones are further directed to a second dialyser that is incorporated in series with the first dialyser. This enables laboratories to determine samples with a very high chloride content up to 60 g/l simultaneously with calcium by using an automated tandem on-line dialysis technique. The fast and reliable fully automated two-component flow injection procedure operated at a sampling frequency of 90 samples per hour and the results obtained for chloride and calcium in industrial effluents compared well with those obtained by standard methods.     

Performance characteristics of a new prototype for a portable GC using ambient air as carrier gas for on-site analysis

The performance characteristics of a portable GC instrument requiring no compressed gas supplies and using relatively lightweight transportable components for the analysis of volatile organic components in large-volume air samples are described. To avoid the need for compressed gas tanks, ambient air is used as the carrier gas, and a vacuum pump is used to pull the carrier gas and injected samples through the wall-coated capillary column and a photoionization detector (PID). At-column heating is used eliminating the need for a conventional oven. The fused silica column is wrapped with heater wire and sensor wire so that heating is provided directly at the column. A PID is used since it requires no external gas supplies and has high sensitivity for many compounds of interest in environmental air monitoring. In order to achieve detection limits in the ppb range, an online multibed preconcentrator containing beds of graphitized carbons and carbon molecular sieves is used. After sample collection, the flow direction through the preconcentrator is reversed, and the sample is thermally desorbed directly into the column. Decomposition of sensitive compounds during desorption is greater with air as the carrier gas than with hydrogen.     

Sapphire sample carriers for silicon determination by total-reflection X-ray fluorescence analysis

Sapphire is presented as a new sample carrier material for total-reflection X-ray fluorescence spectrometry (TXRF). A comparison with conventional sample carrier materials such as quartz glass, Perspex®, glassy carbon and boron nitride demonstrates that sapphire has all the physical and chemical properties required for TXRF micro and trace analysis. Moreover, sapphire sample carriers allow the determination of silicon in many matrices in a comparatively simple way. Especially for airborne particulate matter, acid digestion can be avoided by cool-plasma ashing of suitable filter materials directly on the sample carrier. This technique has been successfully applied to environmental samples.     

Sulfadiazine-selective determination in aquaculture environment: selective potentiometric transduction by neutral or charged ionophores

Solid-contact sensors for the selective screening of sulfadiazine (SDZ) in aquaculture waters are reported. Sensor surfaces were made from PVC membranes doped with tetraphenylporphyrin-manganese(III) chloride, α-cyclodextrin, β-cyclodextrin, or γ-cyclodextrin ionophores that were dispersed in plasticizer. Some membranes also presented a positive or a negatively charged additive. Phorphyrin-based sensors relied on a charged carrier mechanism. They exhibited a near-Nernstian response with slopes of 52 mV decade⁻¹ and detection limits of 3.91 × 10⁻⁵ mol L⁻¹. The addition of cationic lipophilic compounds to the membrane originated Nernstian behaviours, with slopes ranging 59.7-62.0 mV decade⁻¹ and wider linear ranges. Cyclodextrin-based sensors acted as neutral carriers. In general, sensors with positively charged additives showed an improved potentiometric performance when compared to those without additive. Some SDZ selective membranes displayed higher slopes and extended linear concentration ranges with an increasing amount of additive (always <100% ionophore). The sensors were independent from the pH of test solutions within 2-7. The sensors displayed fast response, always <15 s. In general, a good discriminating ability was found in real sample environment. The sensors were successfully applied to the fast screening of SDZ in real waters samples from aquaculture fish farms. The method offered the advantages of simplicity, accuracy, and automation feasibility. The sensing membrane may contribute to the development of small devices allowing in locus measurements of sulfadiazine or parent-drugs.     

Hydrogen and methane sorption in dry and water-loaded multiwall carbon nanotubes

Both H2 and CH4 are clean energy sources. Adsorption was considered a measure to enhance their storage, and many efforts have been dedicated to creating novel materials including carbon nanotubes as efficient carriers for them. In order to understand the uptake mechanism and the viability of practical application, eight adsorption isotherms of H2 on a sample of multiwall carbon nanotubes were collected. The heat of adsorption was determined and an isotherm model was presented. Isotherms of CH4 on the same sample were also collected. While the adsorption on dry samples behaves similarly to that of H2, the sorption behavior of CH4 in the water-loaded sample is quite different and five times higher uptake capacity was observed in the wet sample due to the formation of methane hydrates. However, carbon nanotubes are unlikely to be used as an energy carrier due to its limited surface area and pore volume.     

Comparison of synchrotron radiation total reflection X-ray fluorescence excitation–detection geometries for samples with differing matrices

The linear polarization of synchrotron radiation (SR) in the orbital plane leads to a background reduction in total reflection X-ray fluorescence (TXRF) analysis if a side-looking detector is used. The optimum orientation of the sample carrier in a SR-TXRF experiment, however, is determined by a trade-off between the exploitation of the linear polarization, the efficiency of excitation and the solid angle of detection and depends on the nature and size of the sample. SR-TXRF measurements on different sample types and using different reflector orientations have been carried out at the Hamburger Synchrotronstrahlungslabor bending magnet beamline L. A NIST standard water sample, a steel sample and an oil standard were analyzed with both a horizontal and a vertical sample carrier orientation. Strongly scattering samples led to lower detection limits with a horizontal reflector whereas weakly scattering samples showed lower detection limits with a vertical reflector configuration. On an intentionally contaminated wafer absolute detection limits of 6.6 fg for Ni could be extrapolated.     

Turbidimetric determination of sulphate in plant digests and natural waters by flow injection analysis with alternating streams

An improved flow injection system with alternating streams of reagents is described for the turbidimetric determination of sulphate. Samples are injected into an inert carrier stream which is mixed with barium chloride to form a barium sulphate suspension. The range of the method can be extended to low concentrations by continuously adding sulphate to the sample carrier stream. System performance is improved by automatic alternate pumping of the reagent stream and an alkaline EDTA solution at high flow rate. All operations are controlled by an electronically-operated proportional injector-commutator. Even after routine analysis of 3000 samples of natural waters and plant digests, baseline drift was not observed. The proposed method is suitable for 120 samples per hour with a relative standard deviation less than 1% for sulphate concentrations in the range 1–30 ppm (waters) or 5–200 ppm (plant digests). The results compare well with those obtained by standard manual procedures.     

Isoelectric focusing of membrane proteins: high resolution separation of myelin proteins

A mixture of the nonionic detergent Triton X-100, the zwitterionic detergent 3-[(cholamidopropyl)dimethylammonio]-1-propanesulphonate (CHAPS), 9M urea and carrier ampholytes was found comparable to media containing sodium dodecyl sulfate in the capacity for solubilization of myelin proteins, including the highly hydrophobic proteolipid protein. The solubilized sample was incorporated into the polymerization mixture before moulding an ultrathin gel, with heat convection characteristics allowing a high wattage to be applied, thus allowing fast separation with high resolving power. Since the most basic protein in myelin focuses at a pH greater than 10, fast separation is essential in order to minimize decay of the cathodic end of the pH gradient.     

A thermal model and experimental procedure for a point-source approach to determining the thermal properties of drill cuttings

This paper discusses a new procedure for calculating the conductivity and volumetric heat capacity of drill cuttings from boreholes, an important factor when designing shallow geothermal systems. The experiment in question consists of placing 55–65 kg drill cutting samples inside a container, along with a heat source (point source assumed), and arranging temperature sensors, connected to a data logger, at known distances from the source. A mathematical method for determining the conductivity and volumetric heat capacity associated with this experiment is described.     

Basic aspects of stop-flow split injection

Summary Major concerns in the development of the stop-flow split injection are discussed. Split ratio fluctuation caused by the pressure wave, solvent recondensation and gas viscosity change can be substantially diminished through the formation of a nearly uniform gaseous sample plug. Instrumental variables exerting influence on the accuracy of quantitation were studied. Higher injector temperature and the use of a carrier gas with higher heat conductivity benefit the quick vaporization of the sample liquid, and thus, help in the formation of a sample plug with more unformity.     

Spectropotometric Determination of Cyanide by Flow Injection Analysis

Abstract

The flow injection technique is shown to provide fast, reliable, and sensitive determination of cyanide. Spectrophotometric detection in the ultraviolet region at 267 nm was used for measuring the absorbance of tetracyanonickelate (II) complex ion. The nickel carrier stream and the sample solutions were buffered at pH 10 (ammoniacal buffer). The method has a detection limit of 0.2 ppm cyanide. At a sampling rate of 90 samples per hour, with 60 μl sample injections, high reproducibility of measurements was achieved, with about 1% relative standard deviation. The effects of sample volume, flow rate, coil length, and anions interference on the FIA-spectrophotometeric signals are reported.     

Fabrication of bimetallic microfluidic surface-enhanced Raman scattering sensors on paper by screen printing

Au–Ag bimetallic microfluidic, dumbbell-shaped, surface enhanced Raman scattering (SERS) sensors were fabricated on cellulose paper by screen printing. These printed sensors rely on a sample droplet injection zone, and a SERS detection zone at either end of the dumbbell motif, fabricated by printing silver nanoparticles (Ag NPs) and gold nanoparticles (Au NPs) successively with microscale precision. The microfluidic channel was patterned using an insulating ink to connect these two zones and form a hydrophobic circuit. Owing to capillary action of paper in the millimeter-sized channels, the sensor could enable self-filtering of fluids to remove suspended particles within wastewater without pumping. This sensor also allows sensitive SERS detection, due to advantageous combination of the strong surface enhancement of Ag NPs and excellent chemical stability of Au NPs. The SERS performance of the sensors was investigated by employing the probe rhodamine 6G, a limit of detection (LOD) of 1.1 × 10⁻¹³ M and an enhancement factor of 8.6 × 10⁶ could be achieved. Moreover, the dumbbell-shaped bimetallic sensors exhibited good stability with SERS performance being maintained over 14 weeks in air, and high reproducibility with less than 15% variation in spot-to-spot SERS intensity. Using these dumbbell-shaped bimetallic sensors, substituted aromatic pollutants in wastewater samples could be quantitatively analyzed, which demonstrated their excellent capability for rapid trace pollutant detection in wastewater samples in the field without pre-separation.