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The presence of artificial and natural radioactivity in the environment is currently a topic of great relevance and ecological interest, even in human health issue, due to the increase of different anthropogenic activities. The use of multicommuted flow analysis techniques (e.g. Multi-Syringe Flow Injection Analysis - MSFIA, Lab-On-Valve - LOV and Lab-In-Syringe - LIS) has allowed the automation of radiochemical procedures to separate and preconcentrate radionuclides in environmental and biological samples. In comparison with the manual approach commonly used in routine analysis for radioactivity monitoring, the automation has enabled the development of highly reproducible methodologies with a great analysis frequency. Moreover, during the analytical procedure, the intervention of the analyst is drastically reduced, minimizing the radiological risk. The automation also offers significant advantages such as minimum consumption of time and reagents, reducing the cost and the generation of waste, contributing to the green chemistry. In this review, several multicommuted flow analysis techniques (MSFIA, LOV and LIS) reported in the last decade applied for the development of automatic sample treatment methodologies, used to separate, preconcentrate and quantify 90Sr, 99Tc, natural U and 226Ra in biological and environmental samples are described and critically compared.

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This paper presents a fast and automatic flow-based method to extract 131I from biological samples and hospital waste, previous to liquid scintillation detection. 131I is a radionuclide extensively used in Nuclear Medicine due to their beta and gamma disintegrations, whereby hospitals have to manage the associated waste generation. The automatic developed system is based on Lab-On-Valve (LOV) flow-technique exploiting Cl-resin (135 mg per extraction). This methodology allows performing sample extractions and measurements on the same day, since the extraction frequency takes 1.4-4 h-1, depending on the analysed sample volume, plus up to 2 h of measurement for each vial. 131I is retained as iodine ion and eluted with sodium sulphide 0.2 mol L-1. The maximum sample volume that can be preconcentrated is 20 mL, reaching an extraction efficiency of 85 ±â€¯5%. The minimum detectable activity (MDA) is 0.05 Bq, showing a precision of 7% RSD (n = 5). Both, biological samples (urine and saliva) and hospital waste samples can be satisfactorily analysed by the proposed system, obtaining recoveries between 90 and 110%. The developed method is then suitable to implement in hospitals, improving the surveillance of the 131I environmental release.

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This paper proposes the use of a multisyringe flow injection analysis (MSFIA) system for inorganic antimony speciation analysis, trimethyl antimony(V) and determination of total antimony in soil samples using hydride generation atomic fluorescence spectrometry (HG-AFS). Total antimony has been determined after reduction of antimony(V) to antimony(III) using potassium iodide and ascorbic acid. For determination of total inorganic antimony the sample is percolated in a mini-column containing the Dowex 50W-X8 resin for retention of the organic species of antimony. Antimony(III) is quantified in presence of 8-hydroxyquinoline as masking agent for antimony(V) after an extraction step of the organic antimony species using the also same mini-column. The trimethyl antimony(V) content is found by difference between total antimony and total inorganic antimony. By other hand, antimony(V) is quantified by difference between total inorganic antimony and antimony(III). The analytical determinations were performed using sodium tetrahydroborate as reducing agent. The optimization step was performed using two-level full factorial design and Doehlert matrix involving the factors: hydrochloric acid and sodium tetrahydroborate concentrations and sample flow rate. The optimized experimental conditions allow the antimony determination utilizing the external calibration technique with limits of detection and quantification of 0.9 and 3.1ngg-1, respectively, and a precision expressed as relative standard deviation of 3.2% for an antimony solution of 5.0µgL-1. The method accuracy was confirmed by analysis of the soil certified reference material furnished from Sigma-Aldrich RTC. Additionally, addition/recovery tests were performed employing synthetic solutions prepared using trimethyl antimony(V), antimony(III), antimony(V) and five soil samples. The antimony extraction step was performed in a closed system using hydrochloric acid, ultrasonic radiation and controlled temperature. The method proposed was applied for analysis of thirteen soil samples collected in different sites of the Balearic Islands, Spain, and the results obtained varied from 19 to 46ngg-1 for trimethyl antimony(V) and from 113 to 215ngg-1 for total inorganic antimony. The concentrations obtained to antimony(V) were always higher than for antimony(III) in all the analyzed samples.

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This paper proposed a multisyringe flow injection analysis (MSFIA) system for antimony, arsenic and selenium determination in peanut samples by hydride generation atomic fluorescence spectrometry (HG-AFS). The optimization step of the hydride generation was performed using a two-level full factorial design involving the parameters: hydrochloric acid, sodium tetrahydroborate and potassium iodide concentrations. So, using the chemical conditions optimized, this method allows the determination of these elements employing the external calibration technique using aqueous standards with limits of detection and quantification of 0.04 and 0.14µgL(-1) for antimony, 0.04 and 0.14µgL(-1) for arsenic and 0.14 and 0.37µgL(-1) for selenium, respectively. Additionally, the effect of vanadium, chromium, cobalt, nickel, zinc, copper, iron and molybdenum on the generation of chemical vapour was also studied. The precision expressed as relative standard deviation varied from 1.2 to 3.6% for antimony, 1.8-3.9% for arsenic and 1.8-2% for selenium. The accuracy for arsenic and selenium was confirmed using the certified peach leaves reference material SRM 1547 produced by National Institute of Standard and Technology. The proposed method showed 45 injection throughput (h(-1)) using 1.6mL sample volume for each element, 0.8mL NaBH4 0.5% (w/v) containing NaOH 0.05% (w/v), 0.8mL HCl 5M and 0.4mL KI 14% (w/v) containing L-ascorbic acid 2.5% (w/v). The method was applied to the determination of antimony, arsenic and selenium in peanut samples, which were firstly lyophilized and afterward digested using microwave assisted radiation. Six samples were analyzed and the contents of the elements found were: 28.7-41.3µgkg(-1) for arsenic, 86.4-480.1µgkg(-1) for selenium and 32.6-52.4µgkg(-1) for antimony. Addition/recovery tests were also performed to confirm the method accuracy for the three elements.

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Hydride generation (HG) of lead technique presents interferences from foreign ions of complex matrix samples. In order to minimize these interferences, the effect of masking agents such as KI, L-cysteine, and 1,10-phenanthroline was studied in the absence and in the presence of selected interfering species (As, Cr, Cu, and Fe). Different modes of addition of masking agents were accomplished, that is, to either sample or KBH4 reducing solution. The lead determinations were performed using a flow injection analysis (FIA) system coupled to HG and atomic fluorescence spectrometry (AFS). The linearity of calibration curves (1-10 µg Pb L(-1)) was not affected by the addition of the masking agents. The use of KI in the reducing solution diminished interferences from concentrations of As and Cu, while 1,10-phenanthroline showed a positive effect on the interference by As. Moreover, Cr and Cu appeared to be the most serious interfering ions for plumbane (PbH4), because they drastically reduced the analytical signal of lead. Fe did not present any interference under the employed experimental conditions, even at high levels. The accuracy was established through the analysis of certified reference material (i.e., BCR-610, groundwater) using KI as masking agent. The detection limit reached by FIA-HG-AFS proposed methodology was 0.03 µg Pb L(-1).

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An automatic system based on multisyringe flow injection analysis (MSFIA) and lab-on-valve (LOV) flow techniques for separation and pre-concentration of (226)Ra from drinking and natural water samples has been developed. The analytical protocol combines two different procedures: the Ra adsorption on MnO2 and the BaSO4 co-precipitation, achieving more selectivity especially in water samples with low radium levels. Radium is adsorbed on MnO2 deposited on macroporous of bead cellulose. Then, it is eluted with hydroxylamine to transform insoluble MnO2 to soluble Mn(II) thus freeing Ra, which is then coprecipitated with BaSO4. The (226)Ra can be directly detected in off-line mode using a low background proportional counter (LBPC) or through a liquid scintillation counter (LSC), after performing an on-line coprecipitate dissolution. Thus, the versatility of the proposed system allows the selection of the radiometric detection technique depending on the detector availability or the required response efficiency (sample number vs. response time and limit of detection). The MSFIA-LOV system improves the precision (1.7% RSD), and the extraction frequency (up to 3 h(-1)). Besides, it has been satisfactorily applied to different types of water matrices (tap, mineral, well and sea water). The (226)Ra minimum detectable activities (LSC: 0.004 Bq L(-1); LBPC: 0.02 Bq L(-1)) attained by this system allow to reach the guidance values proposed by the relevant international agencies e.g. WHO, EPA and EC.

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A new, fast, automated and inexpensive sample pre-treatment method for (99)Tc determination by inductively coupled plasma-mass spectrometry (ICP-MS) detection is presented. The miniaturized approach is based on a lab-on-valve (LOV) system, allowing automatic separation and preconcentration of (99)Tc. Selectivity is provided by the solid phase extraction system used (TEVA resin) which retains selectively pertechnetate ion in diluted nitric acid solution. The proposed system has some advantages such as minimization of sample handling, reduction of reagents volume, improvement of intermediate precision and sample throughput, offering a significant decrease of both time and cost per analysis in comparison to other flow techniques and batch methods. The proposed LOV system has been successfully applied to different samples of environmental interest (water and soil) with satisfactory recoveries, between 94% and 98%. The detection limit (LOD) of the developed method is 0.005 ng. The high durability of the resin and its low amount (32 mg), its good intermediate precision (RSD 3.8%) and repeatability (RSD 2%) and its high extraction frequency (up to 5 h(-1)) makes this method an inexpensive, high precision and fast tool for monitoring (99)Tc in environmental samples.

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A fully automated on-line system for monitoring the photocatalytic degradation of herbicides was developed using multisyringe flow injection analysis (MSFIA) coupled to a solid phase extraction (SPE) unit with UV detection. The calibration curves were linear in the concentration range of 100-1000 µg L(-1) for 3,6-dichloro-2-methoxybenzoic acid (dicamba) and 500-3000 µg L(-1) for 2,4-dichlorophenoxyacetic acid (2,4-D), while the detection limits were 30 and 135 µg L(-1) for dicamba and 2,4-D, respectively. The monitoring of the photocatalytic degradation (TiO2 anatase/UV 254 nm) of these two herbicides was performed by MSFIA-SPE system using a small sample volume (2 mL) in a fully automated approach. The degradation was assessed in ultrapure and drinking water with initial concentrations of 1000 and 2000 µg L(-1) for dicamba and 2,4-D, respectively. Degradation percentages of approximately 85% were obtained for both herbicides in ultrapure water after 45 min of photocatalytic treatment. A similar degradation efficiency in drinking water was observed for 2,4-D, whereas dicamba exhibited a lower degradation percentage (75%), which could be attributed to the presence of inorganic species in this kind of water.

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A new automated, sensitive, and fast system for the simultaneous online isolation and preconcentration of lead and strontium by sorption on a microcolumn packed with Sr-resin using an inductively coupled plasma mass spectrometry (ICP-MS) detector was developed, hyphenating lab-on-valve (LOV) and multisyringe flow injection analysis (MSFIA). Pb and Sr are directly retained on the sorbent column and eluted with a solution of 0.05 mol L(-1) ammonium oxalate. The detection limits achieved were 0.04 ng for lead and 0.03 ng for strontium. Mass calibration curves were used since the proposed system allows the use of different sample volumes for preconcentration. Mass linear working ranges were between 0.13 and 50 ng and 0.1 and 50 ng for lead and strontium, respectively. The repeatability of the method, expressed as RSD, was 2.1% and 2.7% for Pb and Sr, respectively. Environmental samples such as rainwater and airborne particulate (PM10) filters as well as a certified reference material SLRS-4 (river water) were satisfactorily analyzed obtaining recoveries between 90 and 110% for both elements. The main features of the LOV-MSFIA-ICP-MS system proposed are the capability to renew solid phase extraction at will in a fully automated way, the remarkable stability of the column which can be reused up to 160 times, and the potential to perform isotopic analysis.

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A novel lab-on-valve system has been developed for strontium determination in environmental samples. Miniaturized lab-on-valve system potentially offers facilities to allow any kind of chemical and physical processes, including fluidic and microcarrier bead control, homogenous reaction and liquid-solid interaction. A rapid, inexpensive and fully automated method for the separation and preconcentration of total and radioactive strontium, using a solid phase extraction material (Sr-Resin), has been developed. Total strontium concentrations are determined by ICP-OES and (90)Sr activities by a low background proportional counter. The method has been successfully applied to different water samples of environmental interest. The proposed system offers minimization of sample handling, drastic reduction of reagent volume, improvement of the reproducibility and sample throughput and attains a significant decrease of both time and cost per analysis. The LLD of the total Sr reached is 1.8ng and the minimum detectable activity for (90)Sr is 0.008Bq. The repeatability of the separation procedure is 1.2% (n=10).

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Acute semistatic toxicity tests were carried out for 96 h with first zoeae and young crabs of Chasmagnathus granulata. Survival curves and LC50 (lethal concentration 50, the concentration which produces the death of 50% of the exposed population) indices for copper, zinc, cadmium, and lead were determined. Furthermore, mixture toxicity tests (Cd/Cu and Cd/Zn) with first-stage larvae were also carried out. The LC50-96 h values determined in this study were 1093.4 (881-1319) microg Pb2+ L(-1), 219.2 (188.9-248.9) microg Cu2+ L(-1), 172.1 (141.3-203.6) microg Zn2+ L(-1), and 47.8 (37.9-58.0) microg Cd2+ L(-1) for zoeae I and 130.1 (121.7-139.0) mg Cu2+ L(-1), 51.0 (41.9-61.6) mg Zn2+ L(-1), and 35.7 (30.1-41.9) mg Cd2+ L(-1) for young crabs. The LC50-96 h indices for mixture tests with zoeae I were 260.6 (227.3-286.3) microg Cd2+/Zn2+ L(-1) and 41.3 (37.4-60.7) microg Cd2+/Cu2+ L(-1). Cadmium presented the highest acute toxicity for both stages of the life cycle examined. The toxicity of the metals analyzed followed the order cadmium >zinc>copper>lead. First zoeae were more sensitive than young crabs to acute exposure to all metals analyzed. The young crabs were considered potentially dangerous agents of transference to the associated trophic chain because of their relatively elevated resistance and their capacity to bioaccumulate heavy metals in their tissues. Mixed toxicity tests carried out on first-stage larvae showed different kinds of interactions. Cadmium/copper presented an additive interaction trend while the mixture cadmium/zinc showed an antagonistic interaction.

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