Determination of metallic nanoparticles in soils by means spICP-MS after a microwave-assisted extraction treatment.

Current sample preparation strategies for nanomaterials (NMs) analysis in soils by means single particle inductively coupled plasma mass spectrometry have significant constrains in terms of accuracy, sample throughput and applicability (i.e., type of NMs and soils). In this work, strengths and weakness of microwave assisted extraction (MAE) for NMs characterization in soils were systematically investigated. To this end, different extractants were tested (ultrapure water; NaOH, NH4OH, sodium citrate and tetrasodium pyrophosphate) and MAE operating conditions were optimized by means of design of experiments. Next, the developed method was applied to different type of metallic(oid) nanoparticles (Se-, Ag-, Pt- and AuNPs) and soils (alkaline, acid, sandy, clayey, SL36, loam ERMCC141; sludge amended ERM483). Results show that Pt- and AuNPs are preserved and quantitatively extracted from soils in 6 min (12 cycles of 30 s each) inside an 800 W oven by using 20 mL of 0.1 M NaOH solution. This methodology is applicable to soils showing a wide range of physicochemical properties except for clay rich samples. If clay soil fraction is significant (>15%), NMs are efficiently retained in the soil thus giving rise to poor recoveries (<10%). The analysis of labile NMs such as Se- and AgNPs is not feasible by means this approach since extraction conditions favors dissolution. Finally, when compared to current extraction methodologies (e.g., ultrasound, cloud point extraction, etc.), MAE affords better or equivalent accuracies and precision as well as higher sample throughput due to treatment speed and the possibility to work with several samples simultaneously.

Microwave-sustained inductively coupled atmospheric-pressure plasma (MICAP) for the elemental analysis of complex matrix samples.

Microwave induced plasma optical emission spectrometry (MIP-OES) has gained widespread attention in the last few years for trace elemental analysis. Among the new generation of MIPs it is worth to mention the microwave-sustained inductively coupled atmospheric-pressure plasma (MICAP) for which previous works have shown similar detection capabilities to those afforded by ICP-OES. Nevertheless, this instrument has not been applied yet to complex matrix sample analysis. Therefore, the goal of this work is to evaluate MICAP-OES performance (e.g., analytical figures of merit, matrix effects, etc.) for elemental analysis of samples of different nature (e.g., environmental, food and polymers). To this end, both spectral and non-spectral interferences were investigated for 19 elements (Ag, Al, As, B, Ca, Cd, Co, Cr, Cu, Fe, Ga, In, Mg, Mn, Ni, Pb, Sr, Tl, Zn) in the presence of inorganic acid, organic and saline solutions and compared to a 5 % w w-1 HNO3 solution. Unlike previous MIPs, experimental data showed that the optimum nebulizer gas flow rate for a given emission wavelength was mostly independent of matrix characteristics. Regarding matrix effects, this device was highly robust operating both inorganic acid and organic matrices. Interestingly, when operating saline matrices, changes on emission signal by easily ionizable elements were less significant than those early reported by alternative MIP cavities. Moreover, due to MICAP spectrometer design employed allows real-time simultaneous analysis, Rh, Pd, Sc and Y were suitable internal standards to minimize non-spectral interferences. Finally, MICAP-OES can be successfully applied to the elemental analysis of different complex matrix samples (i.e., CRM-DW1 Drinking water; BCR-146 Sewage sludge industrial; BCR-185 Bovine liver; BCR-278R Mussel tissue; NIST-1549 Non-fat milk powder; ERM-EC681k Polyethylene (high level) and BCR-483 Sewage sludge amended soil).

Determination of metallic nanoparticles in air filters by means single particle inductively coupled plasma mass spectrometry.

Single particle inductively coupled plasma mass spectrometry (spICP-MS) has been explored for the determination of metallic nanoparticles (NPs) in air. Different extraction strategies (i.e., direct immersion, hard cap espresso, ultrasound-assisted and microwave-assisted extraction) and extracting solvents (i.e., citric acid, trisodium citrate, potassium nitrate, sodium nitrate, thiourea, disodium pyrophosphate and ammonium hydroxide) were investigated for platinum and gold NPs recovery from glass and microquartz fiber filters with a nominal size cut-off of 300 nm. Results show that metallic NPs are preserved and quantitatively extracted from the filter in 4 min inside an 800 W microwave oven by using 40 mL of a 2.0% w w-1 NH4OH solution. For the remaining extraction procedures, either incomplete recoveries or NPs degradation occur. As regards the influence of filter material, microquartz fiber affords better NPs capturing performance than glass fiber ones, enabling the quantification of NPs with diameters above 28 nm. This methodology has been successfully applied to determine PtNPs in filters from environmental monitoring stations and to gain insight into NPs transport through ICP-MS sample introduction system. Care should be taken during spICP-MS calibration since biased results might be obtained due to differences on NPs transport efficiency between standards and samples.

Determination of elemental bioavailability in soils and sediments by microwave induced plasma optical emission spectrometry (MIP-OES): Matrix effects and calibration strategies.

In the past few years, microwave induced plasma optical emission spectrometry (MIP-OES) has generated great interest as an alternative technique to inductively coupled plasma-based techniques due to its lower operational cost. Since MIP-OES suffers from severe matrix effects due to easily ionizable elements (EIEs) (Na, Ca, etc.), it is unclear whether this technique could be employed for elemental bioavailability studies in soils and sediments since the main extractant solutions employed in such works may contain high levels of these elements. Thus, the aim of this work was to evaluate the feasibility of MIP-OES as a detector for such applications. To this end, the influence of different extractant solutions (0.25 mol L-1 MgCl2, 0.25 mol L-1 CaCl2, 0.10 mol L-1 acetic acid, 0.05 mol L-1 Na2EDTA, 0.25 mol L-1 NaNO3, 0.25 mol L-1 NaOAc/HOAc and 0.10 mol L-1 NH2OH·HCl) on the analyte emission of several elements (As, Cd, Co, Cr, Cu, Fe, Mg, Mn, Mo, Ni, Pb, Rh, Se, Sr and Zn) was investigated. Results were compared to those obtained using a reference solution made of 5% w w-1 HNO3 solution. For saline extractant solutions, both the optimum nebulizer gas flow rate (Qg) and analyte emission were modified with regard to the reference solution. In general, the optimum Qg was reduced by between 0.1 and 0.2 L min-1 for both ionic and atomic lines. Under optimum Qg conditions, analyte emission was supressed by saline solutions except for atomic lines with an upper electronic state below 4 eV, which were enhanced. The magnitude of matrix effects was strongly dependent on EIE ionization energy. The lower the ionization energy, the greater the matrix effects were registered. No measurable matrix effects were registered on both Qg and analyte emission within experimental uncertainties for NH2OH·HCl and acetic acid extractant solutions. Experimental data suggest that matrix effects were related to changes in plasma characteristics and the analyte excitation/ionization mechanism. To mitigate matrix effects and improve long-term MIP-OES performance, internal standardization using either Rh (343.489 nm and 369.236 nm) or OH molecular emission band (308.958 nm) was required. This calibration methodology was successfully applied to the study of the elemental bioavailability in soil samples from a vineyard affected by copper-based fungicides and sediment samples from an area affected by mining waste.

The role of Cymodocea nodosa on the dynamics of trace elements in different marine environmental compartments at the Mar Menor Lagoon (Spain).

During mining activities historically developed at Sierra Minera (Cartagena-La Unión, Spain), high amounts of trace elements were discharged to the Mar Menor coastal lagoon mainly through El Beal Wadi. The objective of this study is to establish the role played by the Cymodocea nodosa in the coastal marine dynamics of trace elements at the mouth of the wadi. To this end, the content of nine trace elements (As, Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn) in different marine environmental compartments (i.e. marine and coastal sediments, C. nodosa tissues collected from live seagrass and C. nodosa beach cast litter) at two different locations were determined by inductively coupled plasma atomic emission spectrometry. The results showed that the seagrass C. nodosa could mobilise part of the elements present in marine sediments and water, thereby causing their re-accumulation in the coastal sediments through the C. nodosa beach cast litter.

Coupling dispersive liquid-liquid microextraction to inductively coupled plasma atomic emission spectrometry: An oxymoron?

Coupling dispersive liquid-liquid micro-extraction (DLLME) to inductively coupled plasma atomic emission spectrometry (ICP-AES) is usually troublesome due to the limited plasma tolerance to the organic solvents usually employed for metal extraction. This work explores different coupling strategies allowing the multi-element determination by ICP-AES of the solutions obtained after DLLME procedures. To this end, three of the most common extractant solvents in DLLME procedures (1-undecanol, 1-butyl-3-methyl-imidazolium hexafluorophosphate and chloroform) have been selected to face most of the main problems reported in DLLME-ICP-AES coupling (i.e., those arising from the high solvent viscosity and volatility). Results demonstrate that DLLME can be successfully coupled to ICP-AES after a careful optimization of the experimental conditions. Thus, elemental analysis in 1-undecanol and 1-butyl-3-methyl-imidazolium hexafluorophosphate extracts can be achieved by ICP-AES after a simple dilution step with methanol (1:0.5). Chloroform can be directly introduced into the plasma with minimum changes in the ICP-AES configuration usually employed when operating with aqueous solutions. Diluted inorganic acid solutions (1% w w-1 either nitric or hydrochloric acids) have been successfully tested for the first time as a carrier for the introduction of organic extractants in ICP-AES. The coupling strategies proposed have been successfully applied to the multi-element analysis (Al, Cu, Fe, Mn, Ni and Zn) of different water samples (i.e. marine, tap and river) by DLLME-ICP-AES.

Determination of aflatoxin M1 in milk samples by means of an inductively coupled plasma mass spectrometry-based immunoassay.

An inductively coupled plasma mass spectrometry (ICP-MS)-based immunoassay has been developed to quantify aflatoxin M1 (AFM1) at ultra-trace levels in milk samples. AFM1 detection is carried out by means of a competitive immunoassay using secondary biotinylated antibodies and streptavidin-conjugated Au nanoparticles. After acid addition, nanoparticles are decomposed and Au signal is registered by means of ICP-MS. Results demonstrate that, under optimum conditions, the limit of detection of the immunoassay (0.005µgkg-1) is low enough to quantify AFM1 according to current international policies (including the more restrictive European one). Method accuracy and precision was checked by analyzing an AFM1 certified reference material and different milk samples spiked with known amounts of AFM1. AFM1 recovery values range from 80% to 102% whereas inter-assay and intra-assay precision are lower than 15%. Finally, this immunoassay methodology affords a higher dynamic working range (0.012-2.5µgkg-1) than other immunoassay methodologies described in the literature.

On-line microwave-based preconcentration device for inductively coupled plasma atomic emission spectrometry: application to the elemental analysis of spirit samples.

A microwave-based thermal nebulizer (MWTN) has been employed for the first time as on-line preconcentration device in inductively coupled plasma atomic emission spectrometry (ICP-AES). By the appropriate selection of the experimental conditions, the MWTN could be either operated as a conventional thermal nebulizer or as on-line analyte preconcentration and nebulization device. Thus, when operating at microwave power values above 100 W and highly concentrated alcohol solutions, the amount of energy per solvent mass liquid unit (EMR) is high enough to completely evaporate the solvent inside the system and, as a consequence, the analyte is deposited (and then preconcentrated) on the inner walls of the MWTN capillary. When reducing the EMR to the appropriate value (e.g., by reducing the microwave power at a constant sample uptake rate) the retained analyte is swept along by the liquid-gas stream and an analyte-enriched aerosol is generated and next introduced into the plasma cell. Emission signals obtained with the MWTN operating in preconcentration-nebulization mode improved when increasing preconcentration time and sample uptake rate as well as when decreasing the nozzle inner diameter. When running with pure ethanol solution at its optimum experimental conditions, the MWTN in preconcentration-nebulization mode afforded limits of detection up to one order of magnitude lowers than those obtained operating the MWTN exclusively as a nebulizer. To validate the method, the multi-element analysis (i.e. Al, Ca, Cd, Cr, Cu, Fe, K, Mg, Mn, Na, Pb and Zn) of different commercial spirit samples in ICP-AES has been performed. Analyte recoveries for all the elements studied ranged between 93% and 107% and the dynamic linear range covered up to 4 orders of magnitude (i.e. from 0.1 to 1000µgL(-1)). In these analysis, both MWTN operating modes afforded similar results. Nevertheless, the preconcentration-nebulization mode permits to determine a higher number of analytes due to its higher detection capabilities.

Atomic spectrometry methods for wine analysis: a critical evaluation and discussion of recent applications.

The analysis of wine is of great importance since wine components strongly determine its stability, organoleptic or nutrition characteristics. In addition, wine analysis is also important to prevent fraud and to assess toxicological issues. Among the different analytical techniques described in the literature, atomic spectrometry has been traditionally employed for elemental wine analysis due to its simplicity and good analytical figures of merit. The scope of this review is to summarize the main advantages and drawbacks of various atomic spectrometry techniques for elemental wine analysis. Special attention is paid to interferences (i.e. matrix effects) affecting the analysis as well as the strategies available to mitigate them. Finally, latest studies about wine speciation are briefly discussed.

Ultratrace determination of Pb, Se and As in wine samples by electrothermal vaporization inductively coupled plasma mass spectrometry.

The determination of Pb, Se and As in wine has a great interest due to health risks and legal requirements. To perform the analysis of wine, two considerations must be taken into account: (i) the low concentration level of the analytes; and (ii) the risk of interferences due to wine matrix components. The goal of this work is to evaluate electrothermal vaporization (ETV) sample introduction for ultratrace determination of Pb, Se and As in wine samples by inductively coupled plasma mass spectrometry (ICP-MS). The results obtained with ETV-ICP-MS were compared to those obtained with conventional liquid sample introduction in ICP-MS and electrothermal atomic absorption spectrometry (ETAAS). Analytical figures of merit of ETV sample introduction strongly depend on the amount of wine sample, on the modifier nature (i.e. Pd, ascorbic acid or citric acid) and concentration and on the temperature program. Wine matrix components exert a great influence on analyte transport efficiency. Due to this fact, the analysis of wine cannot be performed by means of external calibration but the standard addition methodology should be used. The determination of Pb and Se in wine by ETV-ICP-MS provides similar results as conventional liquid sample introduction ICP-MS. For As, the concentration values obtained with ETV sample introduction were between two and four times lower than with the conventional system. These differences are related to the lower intensity of polyatomic interferences (i.e. (40)Ar(35)Cl(+) vs. (75)As(+)) obtained for ETV sample introduction when compared to the conventional system. Finally, no differences for Pb determination were observed between ETV sample introduction and ETAAS. Unfortunately, the limits of detection for As and Se in ETAAS were not low enough to quantify these elements in the wine samples tested.

Application of a microwave-based desolvation system for multi-elemental analysis of wine by inductively coupled plasma based techniques.

Elemental wine analysis is often required from a nutritional, toxicological, origin and authenticity point of view. Inductively coupled plasma based techniques are usually employed for this analysis because of their multi-elemental capabilities and good limits of detection. However, the accurate analysis of wine samples strongly depends on their matrix composition (i.e. salts, ethanol, organic acids) since they lead to both spectral and non-spectral interferences. To mitigate ethanol (up to 10% w/w) related matrix effects in inductively coupled plasma atomic emission spectrometry (ICP-AES), a microwave-based desolvation system (MWDS) can be successfully employed. This finding suggests that the MWDS could be employed for elemental wine analysis. The goal of this work is to evaluate the applicability of the MWDS for elemental wine analysis in ICP-AES and inductively coupled plasma mass spectrometry (ICP-MS). For the sake of comparison a conventional sample introduction system (i.e. pneumatic nebulizer attached to a spray chamber) was employed. Matrix effects, precision, accuracy and analysis throughput have been selected as comparison criteria. For ICP-AES measurements, wine samples can be directly analyzed without any sample treatment (i.e. sample dilution or digestion) using pure aqueous standards although internal standardization (IS) (i.e. Sc) is required. The behaviour of the MWDS operating with organic solutions in ICP-MS has been characterized for the first time. In this technique the MWDS has shown its efficiency to mitigate ethanol related matrix effects up to concentrations of 1% (w/w). Therefore, wine samples must be diluted to reduce the ethanol concentration up to this value. The results obtained have shown that the MWDS is a powerful device for the elemental analysis of wine samples in both ICP-AES and ICP-MS. In general, the MWDS has some attractive advantages for elemental wine analysis when compared to a conventional sample introduction system such as: (i) higher detection capabilities; (ii) lower ethanol matrix effects; and (iii) lower spectral interferences (i.e. ArC(+)) in ICP-MS.

New ultrasound assisted chemical oxygen demand determination.

A new method for the chemical oxygen demand (COD) determination assisted by ultrasonic radiation has been evaluated for the first time. The suggested method uses an instrumentation simpler and cheaper than the previous ones used for the same purpose. With this preliminary version of the method the optimized experimental conditions are: high ultrasonic power (143 W, 95% of maximum nominal power; 126.5 W/cm2 of power density); high sulphuric acid concentration (> 60%); and a sonication time of 2 min. Under these conditions this first prototype shows the same limitations as the official COD method as regards the type of organic compounds. It works successfully with easily oxidative organic matter (sodium oxalate, glucose and salicylic acid) but the COD values obtained with more difficult organic matter are poor. When the ultrasonic assisted method is applied to real waste waters the precision is statistically not different to that of the conventional semi-micro method but the COD values obtained lie between 50 and 60% of the values obtained with the conventional semi-micro method. Hence, the use of the ultrasonic radiation for COD determination seems to be an interesting and promising alternative to the conventional ones but still much more research efforts must be done in order to improve the instrumental set-up. The suggested direction of these developments must be a more efficient interaction between the ultrasonic radiation and the sample.