Development of a mobile fast-screening laser-induced breakdown detection (LIBD) system for field-based measurements of nanometre sized particles in aqueous solutions.

Laser-induced breakdown detection (LIBD) is a promising method to detect trace amounts of nanoparticles (NP, <100 nm) in aqueous suspensions. Based on available systems, we developed a mobile LIBD, designed for on-site and on-line measurements. We used the energy ratio of every laser pulse before and after passing the laser beam through the aqueous sample as a new method to detect laser-induced plasma events. The particle size and the particle number density are derived from recorded energy curves. Our LIBD is operated with a Nd:YAG laser at 100 Hz significantly reducing the measurement times compared to other LIBD systems operated at 20 Hz and increasing the capabilities for monitoring purposes. Long-term experiments on water samples revealed losses of NP up to 75% in 15 mL and 35% in 5 L sample containers after 3 months. The size of the particles remained constant (5 L) or slightly decreased (15 mL) indicating significant adsorption of NP to the walls of the sampling containers. Furthermore, we monitored the NP content of water after different purification steps at a drinking water plant (Maennedorf, Lake Zurich, Switzerland). Activated carbon filtration resulted in an increase of the particle size from approximately 20 nm to approximately 75 nm possibly caused by the release of organic fragments derived from the biology within the activated carbon tank. After the final ultrafiltration step the particle size was around 10 nm in agreement with the nominal cutoff of 100 kDa of the membrane. The results underline the strength of a fast-screening LIBD to detect relative changes in NP size and concentration.

Application of laser ablation (LA-ICP-SF-MS) for the elemental analysis of bone and teeth samples for discrimination purposes.

Human bone and teeth fragments can be useful evidence when found in crime scenes and/or mass burials sites. The elemental and isotopic composition of these samples can provide information about environmental exposure events and could also be used to distinguish different individuals. The development and application of robust analytical methods for the quantification of trace elements in these biological matrices may lead to a better understanding of the potential utility of these measurements in forensic analyses. In this paper, we demonstrate the possibility of conducting quantitative analysis of trace metals found in bone remains and suggest a strategy to discriminate between individuals, based on this information. A LA-ICP-SF-MS method using non-matrix matched standard calibration was developed and optimized with bone standard reference materials (SRMs) and subsequently applied to the analysis of real samples. The developed method requires micrograms amount of sample (vs. milligrams required for solution-based analysis) while also reducing the analysis time and resulting in good accuracy (typically <10% bias) and precision (<15% RSD). Additionally, laser ablation allowed using spatial resolution analysis to assess the biogenic elemental composition in buried bone samples. Elemental analysis of bone samples from 12 different individuals provided better discrimination between the individuals when the femur and humerus bones were considered separately (42.7% correct classification with all bones vs. 75.2% and 63.1% for femur bones and humerus bones, respectively). Separation of individuals was achieved by elemental composition of whole teeth samples from 14 individuals, except one case where not all the teeth from the same individual were associated together. Separation of individuals was improved when using elemental composition of the enamel and dentine+cementum layers separately in a set of samples from 7 individuals. These are promising results for the use of elemental analysis by laser ablation ICP-MS for discrimination purposes.

Structure of an F430 variant from archaea associated with anaerobic oxidation of methane.

Microbial mats collected at cold methane seeps in the Black Sea carry out anaerobic oxidation of methane (AOM) to carbon dioxide using sulfate as the electron acceptor. These mats, which predominantly consist of sulfate-reducing bacteria and archaea of the ANME-1 and ANME-2 type, contain large amounts of proteins very similar to methyl-coenzyme M reductase from methanogenic archaea. Mass spectrometry of mat samples revealed the presence of two nickel-containing cofactors in comparable amounts, one with the same mass as coenzyme F430 from methanogens (m/z = 905) and one with a mass that is 46 Da higher (m/z = 951). The two cofactors were isolated and purified, and their constitution and absolute configuration were determined. The cofactor with m/z = 905 was proven to be identical to coenzyme F430 from methanogens. For the m/z = 951 species, high resolution ICP-MS pointed to F430 + CH2S as the molecular formula, and LA-ICP-SF MS finally confirmed the presence of one sulfur atom per nickel. Esterification gave two stereoisomeric pentamethyl esters with m/z = 1021, which could be purified by reverse phase HPLC and were subjected to comprehensive NMR analysis, allowing determination of their constitution and configuration as (17(2)S)-17(2)-methylthio-F430 pentamethyl ester and (17(2)R)-17(2)-methylthio-F430 pentamethyl ester. The corresponding diastereoisomeric pentaacids could also be separated by HPLC and were correlated to the esters via mild hydrolysis of the latter. Equilibration of the pentaacids under acid catalysis showed that the (17(2)S) isomer is the naturally occurring albeit thermodynamically less stable one. The more stable (17(2)R) isomer (80% at equilibrium) is an isolation artifact generated under the acidic conditions necessary for the isolation of the cofactors from the calcium carbonate-encrusted mats.

Laser ablation inductively coupled plasma mass spectrometry for direct analysis of the spatial distribution of trace elements in metallurgical-grade silicon.

The spatial distribution and concentration of impurities in metallurgical-grade silicon (MG-Si) samples (97-99% w/w Si) were investigated by use of laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). The spatial resolution (120 mum) and low limits of detection (mg kg(-1)) for quality assurance of such materials were studied in detail. The volume-dependent precision and accuracy of non-matrix-matched calibration for quantification of minor elements, using NIST SRM 610 (silicate standard), indicates that LA-ICP-MS is well suited to rapid process control of such materials. Quantitative results from LA-ICP-MS were compared with previously reported literature data obtained by use of ICP-OES and rf-GD-OES. In particular, the distribution of element impurities and their relationship to their different segregation coefficients in silicon is demonstrated.

Development and evaluation of a standard method for the quantitative determination of elements in float glass samples by LA-ICP-MS.

Forensic analysis of glass samples was performed in different laboratories within the NITE-CRIME (Natural Isotopes and Trace Elements in Criminalistics and Environmental Forensics) European Network, using a variety of Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) systems. The main objective of the interlaboratory tests was to cross-validate the different combinations of laser ablation systems with different ICP-MS instruments. A first study using widely available samples, such as the NIST SRM 610 and NIST SRM 612 reference glasses, led to deviations in the determined concentrations for trace elements amongst the laboratories up to 60%. Extensive discussion among the laboratories and the production of new glass reference standards (FGS 1 and FGS 2) established an improved analytical protocol, which was tested on a well-characterized float glass sample (FG 10-1 from the BKA Wiesbaden collection). Subsequently, interlaboratory tests produced improved results for nearly all elements with a deviation of < 10%, demonstrating that LA-ICP-MS can deliver absolute quantitative measurements on major, minor and trace elements in float glass samples for forensic and other purposes.

Reconstruction of a case of thallium poisoning using LA-ICP-SFMS.

The unique capabilities of laser ablation in combination with inductively coupled plasma sector field mass spectrometry (LA-ICP-SFMS) were employed to reconstruct details of a homicide by thallium poisoning, which took place 38 years ago in Austria. Thallium was determined in several human bone samples after acid digestion in a microwave oven. The ICP-SFMS results showed that the thallium concentration in the victim's bones was in the range 1.07-2.63 microg g(-1), which is up to 170 times higher compared to concentrations found in bones of persons who have died due to natural causes. The results were in accordance with the values obtained by graphite furnace atomic absorption spectrometry (GF-AAS). Laser ablation ICP-SFMS was applied to assess the time interval between the victim's poisoning and death. Several line scans with a laser spot size of 50 mum were performed on a thumbnail of the poisoned person and on a reference thumbnail by laser ablation ICP-SFMS. Thallium peaks were detected on the nail of the victim at a distance of 2.5 mm from the younger edge of the nail.