Moisés Knochen

A multicommuted flow system for the determination of copper, chromium, iron and lead in lubricating oils with detection by flame AAS

In this work, a flow analysis procedure for the determination of copper, chromium, iron and lead in lubricating oils using flame AAS as detection technique is described. The flow manifold was designed to implement the multicommutation approach and it comprised three 3-way solenoid valves controlled by a personal computer. The flow system presented allowed to process the oil samples to determine wear metals without any prior preparation. Aiming to assess accuracy the results were compared with those obtained by manual procedure using flame AAS. Applying the joint-confidence ellipse test, no significant difference at the 95% confidence level was observed. Other profitable features such as a sample throughput of 50 determinations per hour; relative standard deviations (n = 5) below 2% for Cu, and below 8% for Cr, Fe and Pb; and linear responses in the range 0-40ppm (w/w) (Cu, Fe) and 0-15ppm (w/w) (Cr, Pb) were also achieved.

Pulsed flows in flow analysis: Potentialities, limitations and applications.

In flow analysis, use of a steady and pulseless flow was considered essential for ensuring a reproducible handling of the flowing sample. To this end, peristaltic and syringe pumps have been the propelling device in the vast majority of the flow analysers. Recently, the number of applications involving pulsed flow has been increasing. Most of them refer to use of solenoid pumps, the essence of the so-called multi-pumping flow systems. This review critically discusses the characteristics, potentialities and limitations of the pulsed flow systems, emphasizing the main advantageous characteristics of the streams involved, such as high radial mass transference and good mixing of the fluids. Diverse contributions ranging from instrumentation development to analytical applications are presented.

Multicommutated flow system for the determination of glucose in honey with immobilized glucose oxidase reactor and spectrophotometric detection.

A new automated method for the determination of glucose in honey is proposed. The method is based on multicommutated flow analysis (MCFA) and employs an immobilized glucose oxidase reactor and spectrophotometric detection at 505 nm of the red quinoneimine formed (Trinders method). The calibration curve obeyed a second order equation in the range 0-0.14 g L(-1) (h=-2.2199 C(2)+1.3741 C+0.0077, r(2)=0.9991, where h is the peak height (absorbance) and C the concentration in gL(-1)). The method was validated analyzing eight commercial samples, both by the AOAC 954.11 and 977.20 official methods. According to Students t-test of mean values, at the confidence level of 95% the results obtained with the proposed method were in agreement with those obtained by the official methods. Precision (s(r)(%), n=10) was 3% and the sampling frequency of the system was 20 samples h(-1).

Determination of total selenium by multicommutated-flow hydride generation atomic absorption spectrometry. Application to cow's milk and infant formulae.

A multicommutated flow system was designed and evaluated for the determination of selenium by hydride generation atomic absorption spectrometry (HG-AAS). It was applied to the determination of total selenium in samples of cows milk (fluid and powder) and infant formulae. Linearity was satisfactory in the range up to 27.5 µg L-1 (h = 0.082 C + 0.0033, h = peak-height, absorbance, C = concentration in µg L-1, r2 = 0.999). Detection (3s) and quantification (10s) limits in solution were LD = 0.08 µg L-1 and LQ = 0.27 µg L-1, corresponding to LD = 3.2 µg kg-1 and LQ = 10.8 µg kg-1 in solid samples, and to LD = 0.8 µg L-1, LQ = 2.7 µg L-1 in fluid milk samples. Trueness was verified by analysis (n = 5) of two reference materials (NIST 1549, Non-fat Milk Powder and NIST 1846 Infant Formula). At the 95% significance level, results were statistically equivalent to the certified values. Instrumental precision (sr(%), n = 5) was in the range 1.4% to 11.7%, analytical precision (sr(%), n = 5) being 4.2 and 9.3% respectively for the determination of the above mentioned reference materials. The sampling frequency of the system was 160 hour-1.

Automatic determination of insolubles in lubricating oils by flow injection analysis employing an LED-photometer detector

A flow injection system is presented for the determination of the insolubles content in used lubricating oil samples. The system is based on the injection of an aliquot of the sample in a stream of organic solvent where it is dispersed, and measurement of the scattered radiation (measured as apparent absorbance) in the visible range (lambda=640nm). An LED-based photometer was used for this purpose. The whole system including sample injection and data acquisition was controlled by a personal computer. Calibration curves exhibited good linearity (h=0.415+/-0.016C+0.00+/-0.03, r(2)=0.9995, confidence level of 95%) in the range up to 2.68% (insolubles in pentane). Detection and quantification limits were respectively 0.07% and 0.16% (w/w). The method was validated by analysis of 25 real samples by the proposed method and the FTIR method finding high correlation. Waste generation and reactive consumption is much less than in the official method (ASTM D-893). The proposed method employs 25mL of kerosene per sample while the official method employs 200mL of pentane.

Multiparametric Flow System for the Automated Determination of Sodium, Potassium, Calcium, and Magnesium in Large-Volume Parenteral Solutions and Concentrated Hemodialysis Solutions

A multiparametric flow system based on multicommutation and binary sampling has been designed for the automated determination of sodium, potassium, calcium, and magnesium in large-volume parenteral solutions and hemodialysis concentrated solutions. The goal was to obtain a computer-controlled system capable of determining the four metals without extensive modifications. The system involved the use of five solenoid valves under software control, allowing the establishment of the appropriate flow conditions for each analyte, that is, sample size, dilution, reagent addition, and so forth. Detection was carried out by either flame atomic emission spectrometry (sodium, potassium) or flame atomic absorption spectrometry (calcium, magnesium). The influence of several operating parameters was studied. Validation was carried out by analyzing artificial samples. Figures of merit obtained include linearity, accuracy, precision, and sampling frequency. Linearity was satisfactory: sodium, r 2 >0.999 ( 0.5 – 3.5 g/L), potassium, r 2 >0.996 (50–150 mg/L), calcium, r 2 >0.999 (30–120 mg/L), and magnesium, r 2 >0.999 (20–40 mg/L). Precision ( s r , %, n=5 ) was better than 2.1 %, and accuracy (evaluated through recovery assays) was in the range of 99.8 %– 101.0 % (sodium), 100.8 – 102.5 % (potassium), 97.3 %– 101.3 % (calcium), and 97.1 %– 99.8 % (magnesium). Sampling frequencies ( h −1 ) were 70 (sodium), 75 (potassium), 70 (calcium), and 58 (magnesium). According to the results obtained, the use of an automated multiparametric system based on multicommutation offers several advantages for the quality control of large-volume parenteral solutions and hemodialysis concentrated solutions.

Determination of Zinc-Based Additives in Lubricating Oils by Flow-Injection Analysis with Flame-AAS Detection Exploiting Injection with a Computer-Controlled Syringe

A flow-injection system is proposed for the determination of metal-based additives in lubricating oils. The system, operating under computer control uses a motorised syringe for measuring and injecting the oil sample (200 μL) in a kerosene stream, where it is dispersed by means of a packed mixing reactor and carried to an atomic absorption spectrometer which is used as detector. Zinc was used as model analyte. Two different systems were evaluated, one for low concentrations (range 0–10 ppm) and the second capable of providing higher dilution rates for high concentrations (range 0.02%–0.2% w/w). The sampling frequency was about 30 samples/h. Calibration curves fitted a second-degree regression model (r 2 = 0.996). Commercial samples with high and low zinc levels were analysed by the proposed method and the results were compared with those obtained with the standard ASTM method. The t test for mean values showed no significant differences at the 95% confidence level. Precision (RSD%) was better than 5% (2% typical) for the high concentrations system. The carryover between successive injections was found to be negligible.

LOW COST ANALYZER FOR THE DETERMINATION OF PHOSPHORUS BASED ON OPEN-SOURCE HARDWARE AND PULSED FLOWS

The need for automated analyzers for industrial and environmental samples has triggered the research for new and cost-effective strategies of automation and control of analytical systems. The widespread availability of open-source hardware together with novel analytical methods based on pulsed flows have opened the possibility of implementing standalone automated analytical systems at low cost. Among the areas that can benefit from this approach are the analysis of industrial products and effluents and environmental analysis. In this work, a multi-pumping flow system is proposed for the determination of phosphorus in effluents and polluted water samples. The system employs photometric detection based on the formation of molybdovanadophosphoric acid, and the fluidic circuit is built using three solenoid micropumps. The detection is implemented with a low cost LED-photodiode photometric detection system and the whole system is controlled by an open-source Arduino Uno microcontroller board. The optimization of the timing to ensure the color development and the pumping cycle is discussed for the proposed implementation. Experimental results to evaluate the system behavior are presented verifying a linear relationship between the relative absorbance and the phosphorus concentrations for levels as high as 50 mg L-1.

Determination of Total Selenium in Infant Formulas: Comparison of the Performance of FIA and MCFA Flow Systems

Two flow methods, based, respectively, on flow-injection analysis (FIA) and on multicommutated flow analysis (MCFA), were compared with regard to their use for the determination of total selenium in infant formulas by hydride-generation atomic absorption spectrometry. The method based on multicommutation provided lower detection and quantification limits (0.08 and 0.27 μg L−1 compared to 0.59 and 1.95 μ L−1, resp.), higher sampling frequency (160 versus. 70 samples per hour), and reduced reagent consumption. Linearity, precision, and accuracy were similar for the two methods compared. It was concluded that, while both methods proved to be appropriate for the purpose, the MCFA-based method exhibited a better performance.

Development of a Low-Cost SIA-Based Analyser for Water Samples

An automated multiparametric water analyser was developed and evaluated. The system was based on Sequential Injection Analysis and featured a photometric detection system comprising a tricolour RGB LED source and a photodiode. A program compiled in Visual Basic was used to control the SIA flow system, the LEDs, and the data acquisition and processing. The program loads and executes methods written in ASCII and stored as text files. The system was capable of handling up to four methods simultaneously. When used to carry out methods based on the APHA standard methods, the figures of merit obtained were considered satisfactory for the purpose. The total cost was under US