Coating of borosilicate glass containers for preventing contamination in trace element analysis

Pyrex glass dishes are coated with amorphous 78 SiO₂—21 ZrO₂—1 Na₂0 (mol %) films ca. 50 nm thick. The coated dishes possess reasonable chemical resistance and can be successfully used in the dry ashing of a standard botanical sample for boron determinations and in the evaporation needed for aluminum determination in nitric acid.     

Prevention of contamination and other accuracy risks in voltammetric trace metal analysis of natural waters

Summary General and specific contamination factors affecting accuracy of results in heavy metal analysis at the trace level, with particular reference to the determination of Zn, Cd, Pb, Bi and Cu, are evaluated. Precautions are described to achieve a contamination controlled laboratory in general and manipulation places in particular. Pretreatment and cleaning procedures for sampling bottles and other labware, contamination-free filtration of samples and their long-term storage are dealt with. The recommended procedures ensure a satisfactory elimination of contamination and emphasize the significance of the described preparatory steps and precautions during sample handling, to achieve accurate and consequently relevant analytical results, points which have been frequently underestimated in the past.Taken from the Doctor Thesis L. Mart, RWTH Aachen, 1979     

Prevention of contamination and other accuracy risks in voltammetric trace metal analysis of natural waters

Summary Methods reliably excluding contamination during sampling of surface waters in the open ocean, in coastal waters and estuaries and in inland waters are described in detail. In the open sea the research vessel is a significant source of contamination by heavy metals. Therefore, it must be left in a boat and water is sampled in sufficient distance from the research vessel taking into account all further contamination risks. Sampling in coastal waters is performed preferably from motorboats or cutters (10–25 m length), the size of which permits sampling in front of the boat by means of a sampling bottle attached to a telescope bar. The choice of sampling points must take into account oceanographic parameters, like tidal currents, and ecological aspects, like harbours or estuaries as regions of highlevel pollution. The risks of contamination by the boat are minimised by travelling upstream during sampling in rivers.Taken in part from the Doctor Thesis L. Mart, RWTH Aachen 1979. — Part I: Fresenius Z. Anal. Chem. 296, 350 (1979)     

Instrumental neutron activation analysis for multi-elemental determination in Indian tea samples

Instrumental neutron activation analysis (INAA) was employed to determine concentrations of 19 elements (As, Ba, Br, Ce, Co, Cr, Cs, Fe, K, La, Mn, Na, Nd, Rb, Sc, Sm, Th, Yb and Zn) in a large number (55) of tea samples (from market as well as virgin tea leaves) from different locations in India (Assam, Darjeeling, Munnar and Kangra). The results obtained in the present work are compared with those reported in literature. The concentration levels, their variations with collection locations and the correlations among different elements in these samples are discussed.     

Experience with the sources of contamination when preparing samples for the analysis of trace elements

Summary Modern analysis of trace elements has been carried out for many years. The quality of analysis results however still leaves a lot to be desired. Problems arise from contaminations caused by ubiquitous distribution of the trace elements during preparation of the samples. It is shown where in the laboratory sources of contamination are to be found and how they can be avoided. Experience with sample preparation, a decomposition system with low contamination and cleaning methods are described.

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Erfahrung mit Verunreinigungen bei der Probenvorbereitung für die Spurenelementanalyse

     

Sources of copper and cadmium contamination in small biological samples

Copper and cadmium contamination is investigated in this work with standard reference material no. 1571 (orchard leaf) from the National Bureau of Standards. Consideration is given to possible sources of contamination during the sampling and handling of small biological samples. Acid-washing techniques useful in removing potential contaminants are also discussed. Particular emphasis is placed on the contamination problems related to the analysis of micro-samples.     

On-line preconcentration strategies for trace analysis of metabolites by capillary electrophoresis

Analysis of low concentrations of metabolites is required for new fields of biological research, such as metabolomics. In this review, recent work in our laboratory aimed at developing improved strategies for on-line sample preconcentration of metabolites by capillary electrophoresis (CE) is presented. Dynamic pH junction, sweeping and dynamic pH junction-sweeping represent three complementary methods for electrokinetic focusing of large volumes of sample directly on-capillary. Focusing selectivity and focusing efficiency are two factors that can be used to assess the suitability of each method for different classes of metabolites. Buffer properties can be selected to enhance the focusing of specific types of metabolites based on knowledge of the analyte physicochemical properties. The application of on-line preconcentration CE for trace analysis of metabolites in real samples of interest, such as biological fluids and cellular extracts, is also demonstrated. Under optimum conditions, up to three orders of magnitude increase in concentration sensitivity can be realized for several classes of metabolites, including catecholamines, purines, nucleosides, nucleotides, amino acids, steroids and coenzymes. Recent work on hyphenating on-line preconcentration with multiplexed CE is highlighted as a promising platform for sensitive and high-throughput analyses of metabolites.     

A portable automated system for trace gas sampling in the field and stable isotope analysis in the laboratory

A computer-controllable mobile system is presented which enables the automatic collection of 33 air samples in the field and the subsequent analysis for delta13C and delta18O stable isotope ratios of a carbon-containing trace gas in the laboratory, e.g. CO2, CO or CH4. The system includes a manifold gas source input for profile sampling and an infrared gas analyzer for in situ CO2 concentration measurements. Measurements of delta13C and delta18O of all 33 samples can run unattended and take less than six hours for CO2. Laboratory tests with three gases (compressed air with different pCO2 and stable isotope compositions) showed a measurement precision of 0.03 per thousand for delta13C and 0.02 per thousand for delta18O of CO2 (standard error (SE), n = 11). A field test of our system, in which 66 air samples were collected within a 24-hour period above grassland, showed a correlation of 0.99 (r2) between the inverse of pCO2 and delta13C of CO2. Storage of samples until analysis is possible for about 1 week; this can be an important factor for sampling in remote areas. A wider range of applications in the field is open with our system, since sampling and analysis of CO and CH4 for stable isotope composition is also possible. Samples of compressed air had a measurement precision (SE, n = 33) of 0.03 per thousand for delta13C and of 0.04 per thousand for delta18O on CO and of 0.07 per thousand for delta13C on CH4. Our system should therefore further facilitate research of trace gases in the context of the carbon cycle in the field, and opens many other possible applications with carbon- and possibly non-carbon-containing trace gases.     

Monitoring trace anion contamination in disk drive components

Ion chromatography was used to determine trace anionic contamination on the surface of hard disk drive components. These contaminants can have a detrimental effect on device reliability and yield. Disk drive components were soaked in deionized water and these extracts were analyzed for anions. The anions fluoride, acetate, formate, acrylate, methacrylate, chloride, nitrite, bromide, nitrate, benzoate, sulfate, oxalate, phthalate and phosphate were separated on a high-performance anion-exchange column and determined at concentrations less than 1 microg/l with suppressed conductivity detection. The extract solutions were analyzed either by injecting 1 ml or by preconcentrating 5 ml. We evaluated the performance of both methods.     

Assessment of trace metals contamination in estuarine sediments using a sequential extraction technique and principal component analysis

Fractionation of the metals Cd, Cr, Cu, Ni, Pb and Zn in sediments was performed for samples collected from eight locations in the Poxim river estuary of Sergipe State, northeast Brazil, using the 3-stage sequential extraction procedure proposed by the European Community Bureau of Reference (BCR). The extraction method was found to be satisfactory for analysis of certified reference material BCR-701, with recovery values ranging from 85% (Cu) to 117% (Cr). The detection limits obtained were 0.001 to 0.305 µg g^− 1. Zn exhibited greatest mobility and bioavailability, indicative of anthropogenic sources, while Cr was mainly found in the residual fraction and could be used as an indicator for the contribution from natural sources. Cd, Cu, Ni and Pb were associated with the oxidizable fraction, and Pb, Cr and Ni with the reducible fraction. Principal component analysis (PCA) clearly separated the metals into three groups: I (Zn); II (Pb); III (Cd, Cu, Cr and Ni). These groupings were mainly due to different distributions of the metals in the various fractions, in sediments from the different locations. Risk assessment code (RAC) analysis indicated that although the metals presented a moderate overall risk to the aquatic environment, nickel showed a low risk (RAC < 10%) at three sites, while zinc presented a high risk (RAC > 30%) at four other sites.     

Performance of flowing sample neutron activation analysis technique for determination of multi-elemental content

In order to measure and obtain reliable data about elements via measuring of short-lived isotopes in liquid samples using neutron activation analysis, experiments have been carried out using a flowing sample neutron activation analysis method. During this work the performance and reliability for the proposed method have been tested using synthetic multi elements liquid samples. The radionuclide, associated elements and their concentration level have been measured using a counting system with a fixed dead-time. An HPGe spectrometry system was used to determine the most important γ-ray energies and intensities of these isotopes. The obtained results demonstrated the reliability and accuracy (bias <5 % and zeta score <2) of the tested method for determination the elemental content of liquid samples.     

An innovative Compton suppression spectrometer and its capability of evaluation in multi-elemental neutron activation analysis

A new Compton suppression system was established. A low energy HPGe detector (LO-AX) is used as the analyzing detector. It is completely shielded by a 50%n-type HPGe and two NaI(TI) detectors. Experiments show that a substantial Compton suppression effect is also achieved in the low energy region down to 15 keV. The capability of applying this system in INAA was evaluated for 13 elements (As, Cd, Co, Cr, Hg, Mo, Ni, Sb, Se, Sr, Th, U and Zn) in biological and environmental samples. The benefits and problems of using this Compton suppression spectrometer in INAA are examined for each element.     

Investigation of preconcentration strategies for the trace analysis of multi-residue pesticides in real samples by capillary electrophoresis

In this work, on-line preconcentration strategies were investigated for the multi-residue analysis of pesticides in drinking water and vegetables using micellar electrokinetic chromatography. Among the on-line strategies, sweeping and stacking with reverse migration of micelles (SRMM), with and without the insertion of a plug of water before sample injection, were contrasted. A new version of SRMM was also introduced. The modification consisted of momentarily applying a positive voltage at the inlet vial right after sample has been injected, increasing the efficiency by which the analytes are captured. Nine pesticides from different classes, carbendazim (benzimidazole), simazine, atrazine, propazine and ametryn (triazine), diuron and linuron (urea), carbaryl and propoxur (carbamate), were baseline separated in less than 6 min with a electrolyte composed of 20 mmol l(-1) phosphate buffer at pH 2.5, containing 25 mmol l(-1) sodium dodecyl sulfate and 10% methanol. Limits of detection (LODs) in the order of 2-46 microg l(-1) for the pesticides under investigation were obtained solely using the on-line strategies. Enrichment factors of 3-18-fold were obtained. These factors were computed as the improvement of the concentration LODs with respect to the reference condition (injection of 10 s at 2.5 kPa pressure). The proposed methodologies were applied to the analysis of pesticides in complex matrices such as carrot extracts where the detection of 2.5 microg l(-1) was illustrated. By combining off-line solid-phase extraction and the proposed on-line strategies, the detection of pesticides in drinking water at the 0.1 microg l(-1) level was conceived.     

Internal quality controls applied in inductively coupled plasma mass spectrometry multi-elemental analysis in the second French Total Diet Study

In 2006, the French Food Safety Agency (AFSSA) started the second French Total Diet Study to assess exposure to essential and non-essential elements through dietary intake by analysing 1352 food samples. A total of 21 elements were analysed to date by Inductively Coupled Plasma Mass Spectrometry after closed vessel microwave digestion, in 660 samples corresponding to at half of the study. This work presents and discusses the results of the various internal quality controls (IQC) applied to ensure that the analytical procedure is correctly carried out, from digestion to analysis, and to enable analytical chemists to validate the results obtained. The whole IQC allows to estimate uncertainties according to elements and to select those that should be discarded from the study or only given as indicative values for elements that were not within defined quality limits.     

Sources of trace elements in total diet: A statistical approach

We have collected sixteen total diet samples from two socioeconomic groups in Turkey by duplicate portion techniques. Samples were homogenized with titanium-blade homogenizer, freeze dried and analyzed for their minor and trace elements mostly by neutron activation analysis. Bread and flour samples were also collected from the same regions and analyzed similarly by instrumental neutron activation analysis. We have determined concentrations of more than 25 elements in total diets, bread and flour, and fiber and phytate in total diets. We have determined daily dietary intakes of these population groups, probable source of elements through correlation coefficients, and enrichment factor calculations. This revised version was published online in July 2006 with corrections to the Cover Date.     

An investigation into possible sources of phthalate contamination in the environmental analytical laboratory

A study of common laboratory equipment and components was performed in order to identify sources of contamination of phthalates prior to testing environmental samples for such compounds. A screening study revealed significant leaching from laboratory consumables, such as plastic syringes, pipette tips released maximum leachings of 0.36?µg?cm^?2 diethylhexyl phthalate (DEHP) and 0.86?µg?cm^?2 diisononyl phthalate (DINP), plastic filter holders produced maximum leachings of 2.49?µg?cm^?2 dibutyl phthalate (DBP) from polytetrafluoroethylene (PTFE); specifically 0.61?µg?cm^?2 DBP from regenerated cellulose and 5.85?µg?cm^?2 dimethyl phthalate (DMP) from cellulose acetate and Parafilm® leached levels up to 0.50?µg?cm^?2 DEHP. In addition, a high-temperature bake-out process was found necessary to eliminate quite high levels of two phthalates present in a commercial bulking agent for pressurized liquid extraction.     

Substoichiometry in trace analysis

Substoichiometric methods of analysis are simple in principle and involve the addition of a smaller amount of reagent than is required for complete reaction with the element to be determined. They can be used with great effect in trace analysis.     

A study of trace element contamination in river sediments in Serbia using microwave-assisted aqua regia digestion and multivariate statistical analysis

The aim of this study was the evaluation of the trace element contamination level in sediments of the most important rivers in Serbia and their tributaries. The determination of the aqua regia soluble contents of 12 micro- and macro-elements (Ca, Cd, Co, Cr, Cu, Fe, Mn, Pb, Ni, Zn, Be and V) in sediments was developed by the microwave digestion technique combined with inductively coupled plasma atomic emission spectrometry. Correlation analysis and principal component analysis distinguishes factors of lithogenic and anthropogenic origins. The Fe, Mn, Be and V contents are controlled by a regional lithogenic high background factor, while Cd, Cr, Pb, Ni, Zn and Cu are recognized as tracer of pollution. For Co, mixed sources from both lithogenic and anthropogenic inputs were evidenced.The investigated sediment of the major rivers and their tributaries in Serbia showed high concentrations of metals, especially of Cd, Pb, Cu and Zn, which may cause serious environmental impacts. Rivers which flow into the Danube from its entrance into Serbia significantly influence the chemical load of the water and sediments.The experimental study was conducted using two BCR standard reference materials. The calculated accuracy and precision confirmed the good performance of the adopted procedures.