A high-throughput, straightforward procedure for biomonitoring organomercury species in human hair.

Mercury is a pervasive and concerning pollutant due to its toxicity, mobility, and tendency to biomagnify in aquatic and terrestrial ecosystems. Speciation analysis is crucial to assess exposure and risks associated with mercury, as different mercury species exhibit varying properties and toxicities. This study aimed at developing a selective detection method for organic mercury species in a non-invasive biomonitoring matrix like human hair. The method is based on frontal chromatography (FC) in combination with inductively coupled plasma mass spectrometry (ICP-MS), using a low pressure, homemade, anion exchange column inserted in a standard ICP-MS introduction system, without requiring high-performance liquid chromatography (HPLC) hyphenation. In addition to the extreme simplification and cost reduction of the chromatographic equipment, the proposed protocol involves a fast, streamlined and fully integrated sample preparation process (in contrast to existing methods): the optimized procedure features a 15-min ultrasonic assisted extraction procedure and 5 min analysis time. Consequently, up to 100 samples could be analyzed daily, making the method highly productive and suitable for large-scale screening programs in public and environmental health. Moreover, the optimized procedure enables a limit of detection (LOD) of 5.5 µg/kg for a 10 mg hair microsample. All these features undeniably demonstrate a significant advancement in routine biomonitoring practices. To provide additional evidence, the method was applied to forty-nine human hair samples from individuals with varying dietary habits successfully finding a clear correlation between methylmercury levels (ranging from 0.02 to 3.2 mg/kg) in hair and fish consumption, in line with previous literature data.

How to Clean and Safely Remove HF from Acid Digestion Solutions for Ultra-Trace Analysis: A Microwave-Assisted Vessel-Inside-Vessel Protocol.

The complete dissolution of silicate-containing materials, often necessary for elemental determination, is generally performed by microwave-assisted digestion involving the forced use of hydrofluoric acid (HF). Although highly efficient in dissolving silicates, this acid exhibits many detrimental effects (e.g., formation of precipitates, corrosiveness to glassware) that make its removal after digestion essential. The displacement of HF is normally achieved by evaporation in open-vessel systems: atmospheric contamination or loss of analytes can occur when fuming-off HF owing to the non-ultraclean conditions necessarily adopted for safety reasons. This aspect strongly hinders determination at the ultra-trace level. To overcome this issue, we propose a clean and safe microwave-assisted procedure to induce the evaporative migration of HF inside a sealed "vessel-inside-vessel" system: up to 99.9% of HF can be removed by performing two additional microwave cycles after sample dissolution. HF migrates from the digestion solution to a scavenger (ultrapure H2O) via a simple physical mechanism, and then, it can be safely dismissed/recycled. The procedure was validated by a soil reference material (NIST 2710), and no external or cross-contamination was observed for the 27 trace elements studied. The results demonstrate the suitability of this protocol for ultra-trace analysis when the utilization of HF is mandatory.

One-minute highly selective Cr(VI) determination at ultra-trace levels: An ICP-MS method based on the on-line trapping of Cr(III).

An analytical method derived from the coupling of frontal chromatography (FC) with Inductively Coupled Plasma - Mass Spectrometry (ICP-MS) is proposed for the fast determination of Cr(VI) ultra-traces. The insertion of a short, homemade column filled with a strong cationic exchange resin in the flow-path of a commercial ICP-MS allows on-line trapping of cationic Cr(III) and elution of anionic Cr(VI). As a result, only the Cr(VI) front reaches the detector. This separation mechanism enables the highly selective quantification of Cr(VI) ultra-traces (LOD = 0.026 µg/kg - defined as 3 s of 10 replicated measurements of a 0.050 µg/kg solution) over a wide linearity range (tested up to 1024 µg/kg), even in the presence of Cr(III) concentration as high as 50 mg/kg. Key advantages of the proposed method are the extremely short analysis time (one minute), together with the simplicity and cost-effectiveness of the modifications applied over a commercial ICP-MS instrumental configuration. No time- or chemical-consuming pretreatments are needed: it is only necessary to acidify the sample prior Cr(VI) determination, as normally performed for common ICP-MS analysis. The applicability of the method was demonstrated over mineral water samples and toy migration solutions.

Exploiting Laser-Ablation ICP-MS for the Characterization of Salt-Derived Bismuth Films on Screen-Printed Electrodes: A Preliminary Investigation.

The use of insoluble bismuth salts, typically BiPO4, is known to be a viable alternative to classical Bi3+ ion electrochemical reduction for the preparation of bismuth film electrodes (BiFE) on screen-printed electrodes. The freshly prepared electrodes are indefinitely stable, and the active bismuth film is simply formed by in situ reduction. Two aspects are still to be investigated, namely the bismuth distribution on the working electrode and the possible residual presence of the counteranion, namely phosphate. High-vacuum techniques such as electron microscopy or spectroscopy, which are commonly employed for this purpose, cannot be safely used: the bismuth surface is well-known to reconstruct and recrystallize under the electron beam in vacuum. Here, we demonstrate the suitability and the effectiveness of laser ablation ICP-MS (LA-ICP-MS, a technique that vaporizes and analyzes the surface material under flowing helium at atmospheric pressure) for the characterization of BiFE. Fast and stable measurements of bismuth and phosphorous distribution are achieved with the advantage of a minimum alteration of the sample surface, avoiding possible interferences. This investigation evidenced how, upon reductive activation, the bismuth film is distributed with a radial symmetry and the phosphate counteranion is completely absent on the working electrode surface.

Introducing Frontal Chromatography-Inductively Coupled Plasma-Mass Spectrometry as a Fast Method for Speciation Analysis: The Case of Inorganic Arsenic.

A frontal chromatography-ICP-MS method (FC-ICP-MS) is proposed as an innovative approach for fast elemental speciation analysis: inorganic arsenic speciation was selected as the first case study to prove the feasibility of the technique and to explore its potentialities and limits. The principal benefits of the FC-ICP-MS approach are the short analysis time and the very simple instrumental setup. As(III) and As(V) front separation is performed over a strong anion exchanger at pH 7.5. After the optimization of the instrumental setup and the frontal chromatographic parameters, As(III) and As(V) concentrations up to 240 µg/kg can be determined within 120-140 s using different univariate and multivariate calibration approaches. Best results in terms of accuracy in prediction were obtained using the partial least squares (PLS) calibration achieving limits of detection of 0.18 and 0.21 µg/kg for As(III) and As(V), respectively. This approach was also used to establish the figures of merit of the method. The proved feasibility and good performances (in terms of analysis time and accuracy) of this technique lay the groundwork for future applications of FC-ICP-MS for the speciation of other elements.

How to Efficiently Produce Ultrapure Acids.

Subboiling distillation has been used since two decades for the purification of analytical grade acids from inorganic contaminants and demonstrated an efficient method to obtain pure acids starting from reagent grade chemicals. Nevertheless, the effect of the subboiling parameters on the purity of the distilled acids has never been methodically investigated. Aim of the present research is a systematic evaluation of the subboiling distillation protocol for the production of pure hydrochloric and nitric acid. In particular, the effect of the subboiling temperature and the number of subsequent distillations was investigated as these parameters were recognised as the most important factors controlling acid purity, acid concentration, and distillation yield. The concentration of twenty elements in the purified acids was determined by Inductively Coupled Plasma-Mass Spectrometry. As a result, the subboiling temperature (up to 82°C) and the number of subsequent distillations (up to four) were demonstrated not to affect the purity of the distilled nitric and hydrochloric acids. Under normal laboratory conditions, the residual elemental concentrations were in most cases below 10 ng/L in both nitric (2.75% w/w) and hydrochloric (0.1 M) blanks. Ultrapure nitric and hydrochloric acids could accordingly be produced under the most favorable conditions, i.e., the highest temperature and one distillation process only.

A viscous film sample chamber for Laser Ablation Inductively Coupled Plasma - Mass Spectrometry.

Laser Ablation - Inductively Coupled Plasma - Mass Spectrometry (LA-ICP-MS) is a powerful method to determine the elemental composition of solid-state samples as it combines the high sensitivity and isotope selectivity of ICP-MS detection and the simplicity of laser ablation sampling. This technique enables rapid multiple sampling of the analysed material, such as needed for mapping or in-depth profiling applications. However, the duration of these measurements is practically restricted by the time taken for the particle to be transported from the sampling point to the ICP torch. The ablation cell, i.e. the sample holder, should combine high removal rate, high efficiency (i.e. complete transport of the ablated material) and reduced memory effects. These goals may be achieved by carefully designing the geometry of the cell and its gas flow patterns. A new cell design which enables a homogeneous wahout time of around 210 ms from a cylindrical chamber with 70 mm diameter is introduced in this paper. Washout time was determined as the time for the transient signal of 238U from a NIST610 glass standard to fall to 10% of its peak value. This result is achieved by combining a diffused, cylindrical flow pattern with an extraction tube coaxial with the laser beam and fixed to the laser assembly which enables the sampling point to be constantly positioned on the ablation spot. The lower part of the cell is mounted on the x,y stage for sample movement: the cell sealing is warranted by a viscous film junction between the lower and upper cell parts. Optimisation and performances of the apparatus are discussed in detail and performances are compared to existing designs.

Exploiting Chemistry to Improve Performance of Screen-Printed, Bismuth Film Electrodes (SP-BiFE).

Mercury substitution is a big issue in electroanalysis, and the search for a suitable, and less toxic, replacement is still under development. Of all the proposed alternatives, bismuth films appear to be the most viable solution, although they are still suffering some drawbacks, particularly the influence of deposition conditions and linearity at low concentrations. In this paper, the most promising strategies for bismuth film deposition on screen-printed electrodes (surface modifications, polymeric film deposition, insoluble salt precursors) will be evaluated for trace metal analysis. Particular attention will be devoted to bismuth chemistry, aiming to rationalize their electroanalytic performance.

Understanding microwave vessel contamination by chloride species.

Microwaves are widely used to assist digestion, general sample treatment and synthesis. The use of aqua regia is extensively adopted for the closed vessel mineralization of samples prior to trace element detection, leading to the contamination of microwave vessels by chlorine containing species. The latter are entrapped in the polymeric matrix of the vessels, leading to memory effects that are difficult to remove, among which the risk of silver incomplete recoveries by removal of the sparingly soluble chloride is the predominant one. In the present paper, we determined by mass spectrometry that hydrogen chloride is the species entrapped in the polymeric matrix and responsible for vessel contamination. Moreover, several decontamination treatments were considered to assess their efficiency, demonstrating that several cleaning cycles with water, nitric acid or silver nitrate in nitric acid were inefficient in removing chloride contamination (contamination reduction around 90%). Better results (≈95% decrease) were achieved by a single decontamination step in alkaline environment (sodium hydroxide or ammonia). Finally, a thermal treatment in a common laboratory oven (i.e. without vacuum and ventilation) was tested: a one hour heating at 150°C leads to a 98.5% decontamination, a figure higher than the ones obtained by wet treatments which requires comparable time. The latter treatment is a major advancement with respect to existing treatments as it avoids the need of a vacuum oven for at least 17h as presently proposed in the literature.

How reliable are data for the ecotoxicity of trivalent chromium to Daphnia magna?

Risk assessments from the European Union and the World Health Organization report values for acute and chronic toxicity of Cr(III) to Daphnia magna in the range of 0.6 mg/L to 111 mg/L and 0.047 mg/L to 3.4 mg/L, respectively. To understand whether factors other than the use of different test media and data reporting contribute to this variability, the authors tested the acute (48-h) and chronic (21-d) toxicities of Cr(III) to D. magna according to Organisation for Economic Co-operation and Development (OECD) methods. Filterable (0.45-µm) chromium concentrations were measured at 0 h, 6 h, 24 h, and 48 h, the latter value corresponding to the total duration of the acute tests and to the interval between medium renewals in chronic tests. In highly alkaline media (4.9 meq/L), Cr concentrations decreased rapidly below the analytical detection limit, and no toxicity was observed. In less alkaline media (approximately 0.8 meq/L), the decrease in filterable Cr concentrations was inversely proportional to the quantity of added Cr(III). The authors concluded that existing data likely underestimate the ecotoxicity of Cr(III) to D. magna. A reliable assessment of the hazard of Cr(III) to D. magna must consider that exposure concentrations can decrease markedly from the beginning to the end of a test and that medium alkalinity strongly influences the outcome of laboratory toxicity tests.

An analytical method for Fe(II) and Fe(III) determination in pharmaceutical grade iron sucrose complex and sodium ferric gluconate complex.

A robust voltammetric method has been developed and validated for the determination of Fe(II) and Fe(III) in pharmaceutical iron polysaccharidic complexes. Undesirable low molecular weight iron complexes, at concentration about 3% in the pharmaceutical formulation, can be easily determined with good accuracy and precision. This methodology can be proposed as a viable, environmentally sustainable substitute for the conventional Normal Pulse Polarographic method in US Pharmacopeia, with better analytical figures of merit, and reduced Hg consumption. A deeper insight in Fe(II) and Fe(III) composition can be gained by the combined use of a new potentiometric technique after chemical decomposition of the complex.

Monuments as sampling surfaces of recent traffic pollution.

BACKGROUND, AIM AND SCOPE: A new approach towards monuments, considering them as a passive sampler of pollution, is presented. Cultural Heritage objects suffer daily the damages of environmental pollution, especially in those areas interested by heavy traffic. Since monuments undergo only periodic conservation or maintenance works, surfaces are able to accumulate atmospheric deposit and to record changes in its composition. An optimised analytical protocol was developed in order to quantify platinum and rhodium at trace level on surfaces. The two elements have become tracers of automobile emissions in recent years, since the introduction of catalytic converters, and could have catalytic effects on the decay reactions of natural and artificial stone materials. As a first case study, the cement mortar surfaces of a twentieth century monument, the Camerlata Fountain, in Como (Italy) were investigated. MATERIALS AND METHODS: The surfaces of the monument were scraped in areas both exposed to atmosphere and sheltered by the architectural elements of the building. The powders were dissolved by microwave-assisted mineralisation with a solution of HCl and HNO(3). The solution was filtered, irradiated and analysed by adsorptive cathodic stripping voltammetry. The powders were also analysed by infrared spectroscopy and X-ray diffraction in order to determine the chemical and mineralogical composition. RESULTS AND DISCUSSION: An analysis protocol was set up considering the matrix effect and the expected low concentrations of the two metals. The results enlightened variable concentration values and distribution areas of platinum (0.013-45 µg/kg) and rhodium (0.55-274.4 µg/kg), suggesting the ability of artificial stone surfaces to accumulate the two elements. The sample chemical and mineralogical composition was consistent with a typical cement plaster interested by decay phenomena. CONCLUSIONS: This work investigated the relation between Cultural Heritage and pollution by another point of view. The analytical protocol presented in this paper was effective in determining platinum and rhodium in traces on the investigated stone surfaces with negligible matrix effects. RECOMMENDATION AND PERSPECTIVES: The presence of platinum and rhodium on monument surfaces should be of significant interest when planning Cultural Heritage conservation. A better knowledge of the role of the two metals in decay phenomena could impact in a positive way artwork conservation.

Assessment of accuracy and precision in speciation analysis by competitive ligand equilibration-cathodic stripping voltammetry (CLE-CSV) and application to Antarctic samples.

The analytical performances of Competitive Ligand Equilibration with Cathodic Stripping Voltammetric detection of the labile fraction (CLE-CSV) were assessed. This speciation method enables the concentration of natural ligand(s) and their conditional stability constants for the complexation of the investigated metal to be determined through thermodynamic considerations. Literature data were discussed and general trends in the precision of the determined parameters identified: ligand concentrations were affected, on average, by a 10% relative percentage standard deviation (RSD%), whereas conditional stability constants showed much lower precision, with an average RSD% of 50%. New experimental data were collected to obtain a complete assessment of accuracy and precision attainable for the determination of strong ligands at the ultra trace level, enabling the whole protocol to be evaluated. Firstly, the side reaction coefficient alpha for the formation of the complex between the added ligand and the investigated metal (alpha(CuL)) was determined. The method was subsequently applied to the analysis of solution containing ligand at trace levels (5-50 nM) with known complexing characteristics. Copper was used as the model metal ion and ethylenediaminetetraacetic acid (EDTA) and diethylenetriaminepentaacetic acid (DTPA) as the model ligands. Results evidenced that the CLE-CSV protocol is not affected by systematic errors in the determination of both ligand concentration and the conditional stability constants. Good precision is obtained for ligand concentrations, with an average relative standard deviation (RSD%) of 5%; an average RSD% of 23% was calculated for the conditional stability constants. Including the contribution of the uncertainty in the value of alpha(CuL) in the evaluation of the uncertainty in the latter parameter increased the RSD% up to 40%. The CLE-CSV protocol was subsequently applied to the detection of strong ligands in water samples collected in Antarctica: precision was shown to be comparable with literature data.

Problems in the application of the three-step BCR sequential extraction to low amounts of sediments: an alternative validated route.

Poor recoveries are obtained if the BCR three-step sequential extraction is applied to 100 mg specimens rather than to 1 g. It is observed that analytes are lost during each phase separation which is carried out via centrifugation and can be hardly quantitatively performed on 100 mg sediment specimens. An alternative procedure, which is carried out on a single empty SPE column and involves separation by filtration, is developed to solve this problem. The proposed method is validated on 100 mg samples of certified sediment (BCR-701), but could be potentially used for even lower sediment specimens. Problems related to pH stability during step 2 and its influence on recoveries is also reported.

A chemometric approach to the investigation of major and minor ion chemistry in Lake Como (Lombardia, Northern Italy.

A chemometric approach based on Principal Component Analysis (PCA) has been proposed, in order to study chemical features (major and minor ions, total alkalinity, dissolved silica) of surface and deep waters of Lake Como (Northern Italy). The method allowed us to investigate the correlations between the analyzed ions in an easy-to-see way, using bi-dimensional graphs. In wintertime, the ionic composition of Lake Como waters seems to be mainly related to the geological composition of the lake basin, with a crystalline bedrock on the northern side and a sedimentary cover in the southern part. The presence of contaminants such as bromide and nitrite in water columns is also evidenced and discussed.

Differential pulse voltammetric determination of tin in the presence of noble metals.

A voltammetric method for the determination of tin is proposed to minimise interferences from noble metals that are commonly encountered with other analytical techniques. Strong distortions of voltammetric peaks are observed in the presence of platinum. On the basis of a full investigation, the formation of an intermediate Sn(II)-Pt mixed chloro-complex at the electrode surface is identified as being responsible for the platinum interference, as it competes with the normal Sn(IV)-->Sn(0)Hg reduction. The use of a higher scan rate prevents the relatively low reaction kinetics and thus gets rid of this interference. No problems are encountered with other noble metals such as Pd, Ir, Re, Rh and Ru when using the modified method, although a baseline subtraction is necessary for the latter one. The proposed method is validated with real Pt-Sn catalysts.

Rejuvenating old computerized spectrometric instrumentation: discussion of two case histories.

Computerized analytical instruments of late 70's and 80's are facing rapid technological obsolescence, although they are often retaining good analytical performances. Responsibility is to be attributed to the fast advance in computer technology, which is leaving little or no back-compatibility with old standards and data formats. Rejuvenation may be reached by simple hardware and software modifications, to allow data exchange with modern PC's and LIMS. Two typical case histories for spectrometric instrumentation of late 70's are then presented and discussed in a general fashion.

A calibration curve at 2000 meters (A.S.L.): alpine valleys as field laboratories for teaching environmental monitoring to undergraduate students.

High-altitude alpine valleys may be considered as ideal field laboratories for the interdisciplinary teaching of Environmental Sciences to undergraduate students in a Laurea degree, since different typologies of sampling sites (rivers, lakes, glaciers) may be found within walking distance, and students are encouraged to develop cooperative learning activities. Scientific data have been collected by 1st year students at the University of Insubria in Como during a teaching program in Ventina Valley and Caronno Valley near Sondrio (Italy). Analytical and geochemical results will be presented and discussed on the basis of organic deposition and water-rock interactions.