Heavy metal determinations in algae and clams and their possible employment for assessing the sea water quality criteria.

An empirical criterion for a possible classification of sea water quality is proposed. It is based on the knowledge of metal content in algae (Ulva Rigida) and clams (Tapes Philippinarum), two species present in marine ecosystems. The elements considered are Hg, Cu, Pb, Cd, Zn. The analytical technique employed is Differential Pulse Anodic Stripping Voltammetry (DPASV) in the case of Cu, Pb, Cd, Zn, while the determination of mercury is obtained by the Cold Vapour Atomic Absorption Spectroscopy (CV-AAS) technique with SnCl2 as reducing agent. The analytical procedure has been verified on three standard reference materials: Sea Water BCR-CRM 403, Ulva Lactuca BCR-CRM 279 and Mussel Tissue BCR-CRM 278. For all the elements, in addition to detection limits, accuracy and precision are given: the former, expressed as relative error (e), and the latter, expressed as relative standard deviation (Sr), were in all cases lower than 6%.

Heavy metal determination in aquatic species for food purposes.

New analytical procedures and sample mineralizations are proposed regarding the determination of arsenic, selenium, copper, lead, cadmium, zinc and mercury in matrices involved in food chain as mussel, clams and fishes. As regard As, Se, Cu, Pb, Cd and Zn determinations, H2SO4-HNO3 acidic mixture is used for the digestion of each matrix. In the case of Hg the sample digestion is performed using a concentrated suprapure H2SO4-K2Cr2O7 mixture and the results are compared with those from other conventional methods. Differential pulse cathodic (DPCSV) and anodic stripping voltammetry (DPASV) are employed for determining simultaneously selenium, arsenic and copper, lead, cadmium, zinc, respectively, while mercury determination is carried out by the cold vapour atomic absorption spectrometry (CV-AAS) with reduction with SnCl2. The voltammetric measurements were performed using a conventional three-electrode cell and the ammonia-ammonium chloride buffer (pH 9.3) as supporting electrolyte. For all the elements, in addition to the detection limits, precision and accuracy data are also reported: the former, expressed as relative standard deviation (Sr), and the latter, expressed as relative error (e), are in all cases between 3 to 6%.

Quantitative analysis in field-flow fractionation using ultraviolet-visible detectors: an experimental design for absolute measurements

In previous works, it has been shown that a standard ultraviolet-visible detection system can be used for quantitative analysis of heterogeneous systems (dispersed supermicron particles) in field-flow fractionation (FFF) by single peak area measurements. Such an analysis method was shown to require either experimental measurements (standardless analysis) or an accurate model (absolute analysis) to determine the extinction efficiency of the particulate samples. In this work, an experimental design to assess absolute analysis in FFF through prediction of particles' optical extinction is presented. Prediction derives from the semiempirical approach by van de Hulst and Walstra. Special emphasis is given to the restriction of the experimental domain of instrumental conditions within which absolute analysis is allowed. Validation by statistical analysis and a practical application to real sample recovery studies are also given.

Cathodic and anodic stripping voltammetry: simultaneous determination of As-Se and Cu-Pb-Cd-Zn in the case of very high concentration ratios.

Arsenic(III), selenium(IV), copper(II), lead(II), cadmium(II) and zinc(II) are determined in environmental matrices. The voltammetric measurements were carried out using a conventional three-electrode cell and the ammonia-ammonium chloride buffer pH 9.3 as supporting electrolyte. The analytical procedure was verified by the analysis of the standard reference materials Estuarine Sediment BCR-CRM 277 and River Sediment BCR-CRM 320. The precision, expressed as relative standard deviation (s(r)), and the accuracy, expressed as relative error, were, in all cases, less than 5%; the detection limits, for each element and in the experimental conditions employed, were around 10(-9) M. The standard addition technique significantly improved the resolution of the voltammetric method, even in the case of very high metal concentration ratios.

Simultaneous voltammetric determination of toxic metals in sediments.

Voltammetric methods are very suitable, versatile and rapid techniques for the simultaneous metal determination in complex matrices. The work, regarding the determination of As(III), Se(IV) and Mn(II), is a very interesting example of the possibility for simultaneously determining each single element in real samples in a wide range of concentration ratios. The differential pulse (DPV) measurements were carried out using a conventional three-electrode cell, while ammonia-ammonium chloride buffer (pH 9.6) was employed as the supporting electrolyte. The analytical procedure was verified by the analyses of standard reference materials: estuarine sediment BCR-CRM 277 and river sediment BCR-CRM 320. Precision and accuracy, expressed as relative S.D. and relative error, respectively, were in all cases of the order of 3-5%, while the detection limit for each element was around 10(-8) M. The standard addition technique improved the resolution of the voltammetric method, even in the case of very high element concentration ratios.

A new fast and standardless method for direct determination of metals associated with particulate matter in air: avoiding errors in the determination of Pb in an urban environment.

We describe a new method and the relevant instrumentation necessary for its implementation in the analysis of metals associated with particulate matter in air. The procedure can be divided into two steps: in the first step the sample is accumulated in a device through electrostatic precipitation whose center is a graphite tube; in the second step the graphite tube itself is used as an atomization device for the determination of the metals present in the sample through the electrothermal atomic absorption technique. The method is simple, fast, accurate, and inexpensive. Moreover, if the experimental conditions are well chosen, there is no need for calibration, which is very convenient in the case of samples such as particulate matter in the air. The elements that can be determined with the present apparatus are Hg, Cd, Tl, Ag, Mg, and Mn. These are highly or medium volatile because the materials used cannot reach very high temperatures for long periods. The experiments are confined to air, but other gases, in which a corona discharge is possible, would give the same results. With the method proposed, it was possible to show that the official method for Pb determination in the urban environment of Bologna presents a negative systematic error of about 25%.

Experimental measurement of absolute number of atoms vaporized in a graphite cuvette.

A new method based on electrothermal atomic-absorption spectrometry is proposed for the experimental calculation of the product KN(0) where K is a constant which relates the instantaneous absorbance to the instantaneous number of atoms electrothermally atomized in a graphite cuvette, and N(0) is the number of atoms initially deposited in the graphite cuvette. The method is based on measurement of the integrated absorbance A(i) and the average residence time tau(R) of the atoms in the optical path, from an absorbance vs. time curve. The data so obtained can be used to compare the K values with those in the literature or, if K is known, to calculate N(0) under widely different experimental conditions. The ratio A(i)/tau(R) remains constant even if both A(i) and tau(R) change with different heating rates and the final constant temperature of the euvette surface, T(f).

Determination of subnanogram amounts of chromium in different matrices by flameless atomic-absorption spectroscopy.

A carbon rod flameless atomizer is used for the determination of Cr in water, sea-water, sugar, glycine and blood. The reported analytical curves show that the quantitative determination of Cr in these matrices is feasible in the ppM-ppm range. The influence of the most common anionic and cationic interferents is reported.