An automated sequential injection on-line preconcentration procedure for trace metals by using a PTFE bead-packed microcolumn coupled to ICP-MS is described, and used for simultaneous analyses of cadmium and lead. In dilute nitric acid (0.5%, v/v), neutral complexes between the analytes and chelating reagent, diethyldithiophosphate (DDPA), are formed and adsorbed onto the surface of the PTFE beads. The adsorbed complexes are afterwards eluted with 20% nitric acid and the leading part of the eluate (40ml) is stored in a sample loop (SL), the contents of which are subsequently transported, via a direct injection high efficiency nebulizer (DIHEN), into the ICP-MS for quantification. The packed column (PC) generates considerably lower hydrodynamic impedance than other commonly used sorbent columns, while its preconcentration efficiencies, in terms of retention efficiency and enrichment factor, are significantly improved as compared to a knotted reactor (KR). Inherently, the column approach results in low blank values and consequently in low limits of detection (LODs). With a 40s sample loading time at 4.5ml min21, along with a sampling frequency of 18h21, the retention efficiencies/enrichment factors for cadmium and lead were 96%/72 and 104%/81, respectively, versus 45%/34 and 54%/41 for a knotted reactor with similar internal surface area. In addition, the limits of detection (LODs) and precisions were at the same levels, i.e., the LODs were 2.9ng l21 Cd (PC), 3.5ng l21 Cd (KR), 6.0ng l21 Pb (PC) and 4.7ng 121 Pb (KR), while the RSDs were 1.9% (Cd, PC), 2.7% (Cd, KR), 2.2% (Pb, PC) and 2.5% (Pb, KR). The procedure was validated by determination of trace cadmium and lead in certified reference materials and urine samples.

An automated sequential injection on-line preconcentration procedure for determination of trace levels of copper and lead via solvent extraction/back extraction coupled to ICP-MS is described. In citrate buffer of pH 3, neutral complexes between the analytes and the chelating reagent, ammonium pyrrolidinedithiocarbamate (APDC), are extracted into isobutyl methyl ketone (IBMK). The organic phase is separated from the aqueous one by means of a dual-conical gravitational phase separator, and stored in a PTFE holding coil. Afterwards, the organic phase is propelled and mixed with an aqueous back extractant of nitric acid containing Pd (II) ions as stripping agent, thereby facilitating a rapid metal exchange reaction with the APDC ligand and transfer of the analytes back into the aqueous phase. The aqueous phase is separated in a second dual-conical gravitational phase separator, and 30 ml is entrapped in a sample loop, the content of which is subsequently introduced into the ICP-MS, via a direct injection high efficiency nebulizer (DIHEN), for quantification. nrichment factors of 29.6 (Cu) and 23.3 (Pb), detection limits of 17 ng l21 (Cu) and 11ng l21 (Pb), along with a sampling frequency of 13 h21 were obtained at a sample flow rate of 6.0ml min21. The precisions (RSD) at the 0.2mg 121 level were 4.4%(Cu) and 4.8%(Pb), respectively. The applicability of the procedure is demonstrated for the determination of copper and lead in three certified reference materials and a urine sample.

An automated sequential injection hydride generation (HG) atomic fluorescence spectrometric (AFS) method was developed, with the aim of screening blood lead levels for Chinese citizens, especially for children. Lead hydride was generated from acid solution, with potassium ferricyanide as an oxidizing agent, by reaction with alkaline tetrahydroborate solution. The hydride was separated from the reaction medium in a gas–liquid separator (GLS1) and swept directly into the atomizer. A thorough scrutiny was made of the various factors, including the modification of the AFS instrument and related parameters, the various wet digestion protocols, the variables of the flow system and the reaction conditions. Under the optimized conditions the blank signal was satisfactorily minimized, giving rise to a limit of detection of 0.014μgl-1, defined as 3 times the blank standard deviation divided by the slope of calibration graph, and a RSD value of 0.7%(at the 2.0μgl-1 level, n=11), along with a sampling frequency of 120h-1. The sensitivity of the procedure was found to be significantly superior to those obtained by HG-atomic emission spectrometry (AES), direct sampling electrothermal atomic absorption spectrometry (ETAAS), tungsten filament atomizer ETAAS, and quartz tube atomizer HG-AAS; it was even lower than those by in-atomizer-trapping HG-ETAAS and comparable to ICPMS-based methods. The accuracy and practical applicability of the procedure were validated by analysing certified reference materials of frozen cattle blood GBW 09139 and GBW 09140, and further demonstrated by spiking recoveries of lead in human whole blood samples.

Flow injection (FI) analysis, the first generation of this technique, became in the 1990s supplemented by its second generation, sequential injection (SI), and most recently by the third generation (i. e., Lab-on-Valve). The dominant role played by FI in automatic, on-line, sample pretreatments in recent decades is amply demonstrated by the large number of publications to which it has given rise. Among these, its hyphenation with electrothermal atomic absorption spectrometry (ETAAS) is one of the most attractive sub-branches because of the high sensitivity of ETAAS instruments for metal species. After a decade of development, it is apparent from the literature that coupling FI sample pretreatment with ETAAS remains most dynamic in the new millenium; meanwhile, it is exciting to note that some novel trends associated with this subject have also emerged. The aim of this mini-review is thus to illustrate the state-of-the-art progress in implementing miniaturized FI/SI systems for on-line separation and preconcentration of trace metals with detection by ETAAS since 2000. We also discuss future perspectives in this field.

Within the last decade, the first generation of flow injection (FI) has been supplemented by sequential injection (SI), also termed the second generation, and, recently, by the third generation, i.e., SI-Lab-on-Valve (SILOV). As apparent from the literature, FI and/or SI have become dominant as substitutes for labor-intensive, manual, sample-pre-treatment and/or solution-handling procedures prior to analyte detection by inductively coupled plasma mass spectrometry (ICP-MS). The present review presents and discusses the progress of the state of the art in implementing miniaturized FI/SI systems for on-line matrix separation and pre-concentration of trace levels of metals with detection by ICP-MS. It highlights some of the frequently applied on-line, sample-pre-treatment schemes, including solid phase extraction (SPE), on-wall molecular sorption and precipitate/(co)-precipitate retention using a polytetrafluoroethylene (PTFE) knotted reactor (KR), solvent extraction-back extraction and hydride/vapor generation. It also addresses a novel, robust approach, whereby the protocol of SI-LOV-bead injection (BI) on-line separation and pre-concentration of ultra-trace levels of metals by a renewable microcolumn is interfaced to ICP-MS, as conducted in the present authors' group. It discusses the future outlook in this field.