Critical evaluation of key parameters in single particle ICP-MS data processing for the correct determination of platinum nanoparticles in complex environmental and biological matrices.

There is an urgent need for the harmonization of critical parameters in single particle inductively coupled plasma mass spectrometry (SP-ICP-MS) and they have been deeply studied and optimized in the present work using platinum nanoparticles (PtNPs) as a representative case of study. Special attention has been paid to data processing in order to achieve an adequate discrimination between signals. Thus, a comparison between four different algorithms has been performed and the method for transport efficiency calculation has also been thorougly evaluated (finding the use of a well-characterized solution of the same targeted analyte (30 nm PtNPs) as adequate). The best results have been obtained after the application of a deconvolution approach for the data processing and using 5 ms as dwell time and 40,000 data points for data acquisition. Under the optimized conditions, a correct discrimination between NP events and background signal up to 100 or 750 ng L-1 of added ionic Pt was reached for 30 and 50 nm PtNPs, respectively. The suitability of the developed method for the characterization of PtNPs in relevant environmental (water samples) and biological (cell culture media) matrices has also been demonstrated.

Mercury species accumulation and distribution in Typha domingensis under real field conditions (Almadén, Spain).

Monomethylmercury (MeHg) is one of the most toxic and the most commonly occurring organomercury compound and the wetlands are one of the main areas of generation of this Hg form. Concretely, it is in the macrophyte root system where better conditions are given for its generation. However, the knowledge of absorption and subsequent distribution of mercury (Hg) and monomethylmercury in aquatic plants is still limited. Mercury mining district such as Almadén (Ciudad Real, Spain) is a natural laboratory where different rivers flow and the species Typha domingensis Pers. is a common macrophyte which grows in their riverbanks. The aim of the present work is to apply a recently developed method specially designed to analyze Hg species in plant tissues to the different fractions of T. domingensis under real field conditions and to study the accumulation and distribution of Hg species (inorganic Hg and MeHg) within the plant. The results proved that whatever Hg species has preference to be accumulated in the belowground fractions and demonstrated a high efficiency in the accumulation of MeHg.

Fast method for the simultaneous determination of monomethylmercury and inorganic mercury in rice and aquatic plants.

Recent investigations revealed that monomethylmercury (MMHg) can be absorbed and accumulated by plants, i.e. rice crops, thus becoming an important route of human exposure to MMHg through diet. The increasing concern about this fact makes that appropriate analytical methods for Hg speciation in these samples are urgently required. Therefore, the aim of this work has been the development of a fast and sensitive method which enables the simultaneous determination of MMHg and inorganic Hg in rice and aquatic plants. The proposed methodology is based on the extraction of Hg species by closed-vessel microwave heating, subsequent derivatization by ethylation and analysis by gas chromatography coupled to atomic fluorescence detection via pyrolysis (GC-pyro-AFS). A careful optimization of the extraction, using both acid (6N HNO3) and alkaline (tetramethylammonium hydroxide, TMAH) extractants, and derivatization conditions has been carried out. Spiked and unspiked aquatic plants (Typha domingensis) and CRMs certified for Total-Hg (BCR-60, BCR-482 and NCS ZC73027, corresponding to aquatic plant, lichen and rice, respectively) have been used. Under the final optimized conditions the simultaneous determination of MMHg and inorganic Hg can be carried out in less than 40min with no tedious clean-up steps. Quantitative recoveries (from 92% to 101%) were obtained in aquatic plants (Typha domingensis) and CRMs spiked with known concentrations of MMHg. For unspiked BCR-60 and BCR-482, no statistically significant differences (p=0.05) were found in Total-Hg concentrations between those obtained by the sum of species and the certified values for both acid and alkaline extraction. For the analysis of low Hg polluted samples, an additional preconcentration step by evaporation under nitrogen stream was required but adequate blanks were only obtained for acid extraction. Detection limits in the low ng/g range (0.7-1.0ng/g) were consequently achieved for both Hg species in the case of acid extraction and the analysis of NCS ZC73027 gave satisfactory results without statistically significant differences between the found and certified values (p = 0.05).

Multiresidue determination of organochlorines in fish oil by GC-MS: a new strategy in the sample preparation.

A rapid, economic and environmentally friendly analytical methodology has been implemented for the determination of alpha-, beta-, gamma- and delta-HCH, p,p'-DDT, p,p'-DDD and p,p'-DDE, PCBs congeners #28, #52, #101, #153, #138 and #180 and Hexachlorobenzene in fish oil. 1,2,3,4-Tetrachloronaphtalene was used as internal standard. The sample preparation, consisting of a single step of clean-up and fractionation, took place in a column filled with different layers of neutral and sulphuric acid modified silica. The analytes were eluted by vacuum with of hexane. Significant reduction in terms of solvents, sorbents, and analysis time was achieved in comparison with literature. Gas chromatography coupled to mass spectrometry was used for the separation and determination of the analytes. The instrumental limits of detection were from 0.1 to 1.3ngmL(-1) and the response of the detector was linear up to 200ngmL(-1). The separation proved to be precise (RSD<3.7% in peak area) and robust in terms of peak area, peak efficacy and resolution. The methodology was validated with two certified reference materials of cod liver oil, BCR 598 and BCR 349, obtaining no statistically significant differences between the concentrations found and certified. For the analytes that were not certified, aliquots of the reference materials were spiked and the recoveries obtained were satisfactory. These results were consistent with those found previously for DDTs by gas chromatography with an electron-capture detector. The methodology was applied to the analysis of three fish oil pills sold in Spain as a dietary supplement of vitamins and omega-3 fatty acids. The sum of the analytes studied was from 64 to 80ngg(-1). The most abundant compounds are PCBs, followed by DDTs in all samples.

Determination of mercury species in fish reference materials by gas chromatography-atomic fluorescence detection after closed-vessel microwave-assisted extraction.

A simple and rapid method has been developed for speciation analysis of inorganic mercury and monomethylmercury (MMHg) in biological tissues. The procedure is based on the quantitative closed-vessel microwave-assisted leaching of mercury from biological samples with an alkaline extractant. The extracted mercury species are ethylated and analysed by capillary gas chromatography coupled to an atomic fluorescence detector via pyrolysis (CGC-pyro-AFS). The coupling between capillary gas chromatography and atomic fluorescence detector was optimized with the aim of minimizing the detection limits and time necessary for the species-selective determination of mercury compounds. The use of closed-vessel microwave-assisted extraction along with no clean-up steps before the ethylation leads to a significant total analysis time decrease with respect to similar procedures. The detection limit was 2 pg for MMHg (as Hg) and 1 pg for inorganic mercury. The method was validated by the analysis of DORM-2 (dogfish muscle) and DOLT-3 (dogfish liver) certified reference materials. The inorganic mercury and methylmercury concentrations found were in good agreement with the certified values. Recovery studies of fish muscle tissue spiked with inorganic mercury and MMHg were done to check the reliability of the method. In all cases satisfactory recoveries (92-105%) were obtained.